Stable organic-inorganic materials for waveguides, optical devices, and other applications

ABSTRACT

Waveguides having high stability are disclosed (and other devices and materials including but not limited to coatings, passivation materials, glob top materials, underfill materials, materials for IC and other applications, microlenses and any of a wide variety of optical devices) that benefit by being formed of a novel hybrid organic-inorganic material. In one embodiment of the invention, a method for making a waveguide includes: forming a lower cladding layer on a substrate; forming a core layer after the lower cladding layer; and forming an upper cladding layer after the core layer; wherein the lower cladding layer, core layer and/or upper cladding layer comprises a stable material with a relatively high glass transition temperature. Preferably the material is one that does not degrade or otherwise physically and/or chemically change upon further processing or when in use. Preferably the stable waveguide material of the invention can be heated in supercritical water vapor at 2 atm and at 120 C for 2 hours without degradation (e.g. after which optical absorption, polarization dependent loss and/or refractive index change remains unchanged ±5%).

BACKGROUND OF THE INVENTION

[0001] Growing internet and data communications are resulting in theneed for greater numbers and types of optical components withinexpanding optical networks. DWDM systems, or any system that utilizeslight to transmit information, utilize a variety of components forcreating, transmitting, manipulating and detecting light. Such opticaldevice components, also referred to as optoelectronic or photoniccomponents, often comprises at least a portion that is transmissive tolight at particular wavelengths. Fibers and planar light guides areexamples of passive light transmissive optical components within anoptical network. However, light manipulators (components that modify,filter, amplify, etc. light within the optical network) also often haveportions that are transmissive to light, as often do photodetectors andlight emitters.

[0002] Regardless of the type of optical device component, it is usuallydesirable that a material is used that is highly transmissive to thewavelengths used to transmit information through the optical network. Inaddition to low optical absorbance, the material should preferably havelow polarization dependent loss and have low birefringence andanisotropy, and low stress. It is also desirable that the material beeasy to deposit or form preferably at a high deposition rate and at arelatively low temperature. Once deposited or formed, it is desirablethat the material can be easily patterned, preferably directly patternedwithout the need for photoresist and etching steps, and preferablypatterned with small feature sizes if needed. Once patterned, thematerial should preferably have low surface and/or sidewall roughness.

[0003] It is also desirable that such materials be hydrophobic to avoiduptake of moisture (or other fluids) once installed and in use. Thehydrophobicity of a material can be measured by the contact angle madeby a drop of water (having a specific volume) on the material surface.Hydrophobicity is particularly desirable for waveguides and otheroptical devices that are deployed in potentially high humidityenvironments (or other environments where the device could be exposed towater or other liquids or gases that could be absorbed by or otherwisedegrade the device).

[0004] Also, it is important that the material be highly stable with arelatively high glass transition temperature (not degrade or otherwisephysically and/or chemically change upon further processing or when inuse). A common procedure for testing the stability of a material is theso-called “pressure cooker” test—where a material is placed in a wetenvironment at a particular pressure and temperature for a predeterminedperiod of time in order to determine whether the material will degradeunder such conditions. For example, the hybrid material of the inventionon a substrate can be heated in supercritical water vapor at 2 atm andat 120 C for 2 hours without degradation (e.g. after which opticalabsorption, polarization dependent loss and/or refractive index changeremains unchanged ±5%—or preferably ±2%—and, of course, the materialremains on the substrate).

[0005] Often, current materials used for making optical devicecomponents have only one or a few of the above-mentionedcharacteristics. For example, inorganic materials such as silica arerelatively stable, have relatively high glass transition temperatureshave relatively low optical loss. However, silica materials oftenrequire higher deposition temperatures (limiting substrates andcomponents on the substrates) and have lower deposition rates and cannotbe directly patterned. Organic materials such as polymers can bedeposited at lower temperatures and at higher deposition rates, but arerelatively unstable and have lower glass transition temperatures. Whatare needed are materials for optical device components that have alarger number of the preferred characteristics set forth above.

[0006] In the present invention, stable hybrid organic-inorganicmaterials are used for the various applications mentioned above, andothers. The hybrid materials of the invention provide the benefits ofinorganic materials (stability, glass transition tenperature, opticalprofiles, etc.) while also providing the benefits of organic materials(ease of handling and deposition, etc.). Preferably, the hybridmaterials of the invention have an inorganic backbone, such as one madeof a metal or metalloid oxide three dimensional network, with organicsubstituents and cross linking groups (which call be partially or fullyfluorinated).

SUMMARY OF THE INVENTION

[0007] The invention is directed to waveguides and other devices andmaterials (including but not limited to hybrid organic-inorganiccoatings, passivation materials, glob top materials, underfillmaterials, dielectric materials for IC and other applications,microlenses and any of a wide variety of optical devices) that benefitby having both organic and inorganic components, among other things. Inone embodiment of the invention, a method for making a waveguidecomprises: providing a substrate; forming a lower cladding layer on thesubstrate; forming a core layer above the lower cladding layer; andforming an upper cladding layer above the core layer; wherein the lowercladding layer, core layer and/or upper cladding layer is a stable layerthat comprises a material that is capable of being heated insupercritical water vapor at 2 atm and at 120 C for 2 hours after whichoptical absorption, polarization dependent loss and/or refractive indexchange remains unchanged ±5%.

[0008] In another embodiment of the invention, a waveguide comprises: asubstrate; a waveguide layer, wherein the waveguide layer comprises ahybrid organic-inorganic material, wherein the material is capable ofbeing heated in supercritical water vapor at 2 atm and at 120 C for 2hours after which optical absorption, polarization dependent loss and/orrefractive index change remains unchanged ±5%.

[0009] In another embodiment of the invention, an optical devicecomponent, comprises: a substrate; and a waveguide layer, wherein thewaveguide layer comprises a material that is capable of being heated insupercritical water vapor at 2 atm and at 120 C for 2 hours after whichoptical absorption, polarization dependent loss and/or refractive indexchange remains unchanged ±5%.

[0010] In still further embodiments of the invention, the hybrid stablematerial forms part of other devices and materials (including but notlimited to hybrid coatings, passivation materials, glob top materials,underfill materials, dielectric materials for IC and other applications,microlenses and any of a wide variety of optical devices). These otherapplications allow for a layer or complete device that has benefits ofboth organic and inorganic materials.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] COMPOUNDS:

[0012] In this section, compounds are described that can be hydrolyzedand condensed (alone or with one or more other compounds) into a hybridmaterial having a molecular weight of from 500 to 10,000 (preferablyfrom 500 to 5000, or more preferably 500 to 3000), which material can bedeposited by spin-on, spray coating, dip coating, or the like. Suchcompounds are preferably partially or fully fluorinated, though notnecessarily so. The compounds will preferably have an element M selectedfrom groups 3-6 or 13-16 of the periodic table, which element ispreferably tri-, tetra- or penta-valent, and more preferablytetravalent, such as those elements selected from group 14 of theperiodic table. Connected to this element M are from three to fivesubstituents, wherein from one to three of these substituents areorganic groups to be discussed further below, with the remainder being ahalogen or an alkoxy group.

COMPOUND EXAMPLE I:

[0013] A compound is provided of the general formula: R¹MOR³ ₃, where R¹is any partially or fully fluorinated organic group (preferably apartially or fully fluorinated aryl, alkenyl, alkynyl or alkyl group),where M is an element selected from column 14 of the periodic table, andwhere OR³ is an alkoxy group—except where M is S¹, R¹ is perfluorinatedphenyl or perfluorinated vinyl, and OR³ is ethoxy, which, though notnovel per se, can be part of one of the novel methods for making thematerials of the invention as will be discussed further below. R¹ canhave an inorganic component, though if so, a portion should preferablybe a partially or fully fluorinated organic component. In a morepreferred example of this, R¹ comprises a double bond that is capable ofphysical alteration or degradation in the presence of an electron beam,or electromagnetic radiation and a photoinitiator (or sensitizer,photoacid or thermal initiator—to be discussed further below). In thisexample, R¹ could be an alkenyl group such as a vinyl group, or could bean epoxy or acrylate group, that is preferably partially or fullyfluorinated. Such a group, as will be discussed further herein, canallow for crosslinking upon application of an electron beam orpreferably electromagnetic radiation (e.g. directing ultraviolet lightthrough a mask with the material comprising a photoinitiator). In thealternative, R¹ could be an organic group that is (or a hybridorganic-inorganic group that comprises) a single or multi ring structure(an “aryl group”) or an alkyl group of any length, such as from 1 to 14carbon atoms or longer (preferably 4-10)—the alkyl group capable ofbeing a straight or branched chain. If R¹ is a ring structure, or acarbon chain of sufficient length (e.g. 4 (or 5) or more carbons), thensuch an R¹ group can provide bulk to the final material once hydrolyzed,condensed and deposited on a substrate. If R¹ is a ring structure,whether single ring or multi ring, it can have substituents thereon,fluorinated, though not necessarily, such as alkyl or alkenylsubstituents (preferably from 1 to 5 carbons), and where thesubstituents on the ring structure can be at from 1 to 3 locationsaround the ring. R¹ can be a 4 to 8 sided ring structure (preferably 5or 6 sided) which ring structure could comprise N or O. R1 couldcomprise nitrogen, or R¹ can also have an oxygen component, such as acarboxylate group (e.g. acrylate, butenecarboxylate, propenecarboxylate,etc.).

[0014] In the example above, in R¹MOR³ ₃, M can be a tetravalent elementfrom column 14 of the periodic table (e.g. Si or Ge), or a tetravalentelement from column 16—e.g. Se (or a tetravalent early transitionmetal—such as titanium or zirconium). Also, OR³ is an alkoxy group,though preferably one having from 1 to 4 carbon atoms (longer alkoxygroups can be used, but are more expensive). Specific examples include:

Acryltriethoxysilane

Pentafluorophenyltriethoxygermane

Chlorodifluoroacetic acid, triethoxy silyl ester

Perfluoro-3-butene acid, triethoxysilyl ester

Heptafluorotoluenetriethoxysilane

4-triethoxysilyl perfluorostyrene

Tetrafluoroethyltrifluorovinyl ether triethoxysilane

Perfluorobutanetriethoxysilane

Perfluoro-t-butyl triethoxysilane

Perfluorooctyltriethoxysilane

Perfluorohexanetriethoxysilane 2-trifluoromethyl-2-triethoxysilylperfluoro pentane

COMPOUND EXAMPLE II:

[0015] In yet another compound example, a compound is provided of thegeneral formula: R¹MOR³ ₂X, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above, where M is anelement selected from group 14 of the periodic table as mentioned above,where X is a halogen, and where OR³ is an alkoxy group as above. X inthis example is preferably F, Cl, Br or I, and more preferably Cl or Br.Specific examples of compounds within this category include

COMPOUND EXAMPLES III

[0016] In another compound example, a compound is provided of thegeneral formula: R¹MX₂OR³, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above, where M is anelement selected from group 14 of the periodic table as mentioned above,where OR³ is an alkoxy group as above, and where X is a halogen asabove—Except where M is Si, R¹ is perfluorinated phenyl, X is Cl, andOR³ is ethoxy, which, though not novel per se, is novel when used aspart of the methods for making the materials of the invention as will bediscussed further below. Specific examples within this category include

COMPOUND EXAMPLE IV:

[0017] In a further compound example, a compound is provided of thegeneral formula: R¹MX₃, where R¹ is any partially or fully fluorinatedorganic group (preferably a partially or fully fluorinated aryl,alkenyl, alkynyl or alkyl group) as set forth above, where M is anelement selected from group 14 of the periodic table as mentioned above,and where X is a halogen as above—Except where M is S¹, R¹ isperfluorinated phenyl, perfluorinated methyl or perfluorinated vinyl,and X is Cl, which, though not novel per se, are novel when used as partof the methods for making the materials of the invention as will bediscussed further below. (If M is Si and X is Cl, some of these noveltrichlorosilanes could be used for forming self assembled monolayers formaking a surface hydrophobic, preferably by application in the vaporphase to a surface made of silicon and having OH end groups andmoisture.)

[0018] Specific examples within this category include

COMPOUND EXAMPLE V:

[0019] In yet another compound example, a compound is provided of thegeneral formula: R¹R²MOR³ ₂, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹, R² is any partially or fully fluorinated organic group(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl oralkyl group) as set forth above with respect to R¹, or any such organicgroups nonfluorinated, and where R¹ and R² are the same or differentfrom each other, where M is an element selected from group 14 of theperiodic table as mentioned above, and where OR³ is an alkoxy group asabove—except where M is S¹, OR³ is ethoxy and R¹ and R² areperfluorinated phenyl groups, which compound is not novel per se, but isnovel when used as part of the methods for making materials of theinvention as set forth below.

[0020] Specific examples within this category include:

Pentafluorophenyltrifluorovinyldiethoxy- silane

Methylpentafluorophenyldimethoxy- silane

Pentafluorophenyltrifluoromethyl diethoxysilane

Perfluorotoluenetrifluorovinyldiethoxy- silane

Di(perfluorotoluene)diethoxysilane

Perfluorostyreneperfluorotoluenediethoxy- silane

Pentafluorophenylperfluorostyryl- diethoxysilane

Bis(perfluorohexane)diethoxysilane

Perfluorooctyltrifluorovinyldiethoxysilane

Bis(trifluorovinyl)diethoxysilane

Perfluoro(t-butyl)trifluorovinyldiethoxysilane

COMPOUND EXAMPLE VI:

[0021] In another compound example, a compound is provided of thegeneral formula: R¹R²MXOR³, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹, R² is any partially or fully fluorinated organic group(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl oralkyl group) as set forth above with respect to R¹, or any such organicgroups nonfluorinated, and where R¹ and R² are the same or differentfrom each other, where M is an element selected from group 14 of theperiodic table as mentioned above, where OR³ is an alkoxy group asabove, and where X is a halogen. R¹ and R² can be the same or differentfrom each other

[0022] Specific examples within this category include:

COMPOUND EXAMPLE VII:

[0023] In a further compound example, a compound is provided of thegeneral formula: R¹ R²MX₂, where R¹ is any partially or fullyfluorinated organic group (preferably a partially or fully fluorinatedaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹, R² is any partially or fully fluorinated organic group(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl oralkyl group) as set forth above with respect to R¹, or any such organicgroups nonfluorinated, and where R¹ and R² are the same or differentfrom each other, where M is an element selected from group 14 of theperiodic table as mentioned above, and where X is a halogen asabove—Except where M is Si, R¹ and R² are perfluorinated phenyl, and Xis Cl, which, though not novel per se, is novel when used as part of themethods for making the materials of the invention as will be discussedfurther below. Specific examples within this category include:

[0024] As Compounds V-VII have two organic groups, they can be formed byvarious combinations of Methods A, B and/or C (described in furtherdetail below).

COMPOUND EXAMPLE VIII:

[0025] In a further compound example, a compound is provided of thegeneral formula: R¹R² R³MOR³, where R¹, R² and R³ are independently anaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹ and R², and where R¹, R² and R³ can each be the same or differentfrom each other (and preferably at least one of where R¹, R² and R³ ispartially or fully fluorinated), where M is preferably an elementselected from group 14 of the periodic table as above, and where OR³ isan alkoxy group as above. One example is

[0026] though the organic groups need not each be the same as in thisexample, and need not each be fluorinated (though preferably at leastone of the organic groups is fluorinated).

COMPOUND EXAMPLE IX:

[0027] In another compound example, a compound is provided of thegeneral formula: R¹R² R³MX, where R¹, R² and R³ are independently anaryl, alkenyl, alkynyl or alkyl group) as set forth above with respectto R¹ and R², and where R¹, R² and R³ can each be the same or differentfrom each other (and preferably at least one of where R¹, R² and R³ ispartially or fully fluorinated), where M is preferably an elementselected from group 14 of the periodic table as above, and where X is ahalogen as above.

[0028] One example is:

[0029] As Compounds VIII and IX have three organic groups, they can beformed by various combinations of Methods A, B and/or C (which methodsare described in further detail below).

OTHER COMPOUNDS:

[0030] Additional compounds for making the materials of the inventioninclude those having the general formula R¹MHX₂ where R¹, M and X are asabove and H is hydrogen. One example is:

[0031] Other examples, where the fluorinated phenyl group is replacedwith a substituted phenyl, fluorinated alkyl, vinyl, etc. are possible.

[0032] It should be noted that M in the compound formula examples aboveneed not be tetravalent. M can also have other valencies, thoughpreferably tri- or penta-valent. Examples would include early transitionmetals in group 3 or 5 of the periodic table (e.g. Y, V or Ta), orelements in columns 13 (column headed by B) or 15 (column headed by N),such as B, Al or As. In such situations, the compounds above would haveone fewer or one additional alkoxy (OR³), halogen (X) or an organicgroup (R¹ or R² independently from the other organic group(s)). Examplesinclude R¹MOR 3X, R¹MOR³ ₂, R¹MX₂, R¹R²MX, R¹R²MOR³, where M is atrivalent early transition metal (or similar examples with fivesubstituents selected from R¹ and/or R² groups, as well as alkoxy andhalogen groups for pentavalent elements (including metalloids ortransition metals). Such compounds could have the formulaR1_(3-m)MOR3_(m), R1_(5-m)MOR3_(m), R2R1_(4-m)MOR3_(m) or R2R1_(4-m)MOR3_(m). If such tri- or penta-valent elements are used, such acompound would preferably be hydrolyzed and condensed as a dopant,rather than as the main portion of the material at the time ofhydrolysis and condensation (likewise with non-silicon tetravalentelements that form compounds in accordance with the tetravalent examplesabove, such as germanium compounds).

[0033] It should also be noted that the structures illustrated above areexemplary only, as other ring structures (3 sided—e.g. epoxy, or 4 to 8sided—preferably 5 or 6 sided) are possible, which structures caninclude nitrogen or oxygen in or bound the ring. The aryl group can havefrom 1 to 3 substitutents, such as one or more methyl, ethyl, ally,vinyl or other substituents—that can be fluorinated or not. Also, carbonchain R groups can include oxygen (e.g. carboxylate) or nitrogen, orsulpher. If an alkyl group is bound to the silicon (or other M group),it can have from 1 to 4 carbons (e.g. a C2+ straight or C3+ branchedchain), or up to 14 carbons (or more)—if used as a bulk enhancing groupfor later hydrolysis and deposition, 4 or more carbons are preferable.These aryl groups can be fully or partially fluorinated, as can alkenylor alkynyl groups if used.

[0034] Methods of Making the Compounds for Later Hydrolysis andCondensation:

[0035] In a number of the following examples of methods for making thematerials of the invention, “M” is silicon, OR³ is ethoxy, and X is Cl.However, as noted above, other alkoxy groups could easily be used(methoxy, propoxy, etc.), and other group 3-5 or 13-16 elements could beused in place of silicon and other halogens in place of chlorine.Starting materials can vary from tetraethoxy silane, to ethoxy silaneshaving one or more organic groups bound to the silicon, to chorosilaneshaving one or more chlorine groups and/or one or more organic groups, aswell as starting materials having chlorine and alkoxy groups and withone or more organic groups. Any compound examples within Compounds I-IXabove could be used as starting materials—or could be intermediate orfinal compounds as will be seen below. For example,trifluorovinyltriethoxysilane could be a final compound resulting fromreacting a particular trifluorovinyl compound with tetraethoxysilane, ortrifluorovinylsilane could be a starting material that, when reactedwith a particular pentafluorophenyl compound, results inpentafluorophenyltrifluorovinyldiethoxysilane. As mentioned above, it isalso preferred that any organic groups that are part of the startingmaterial or are “added” by chemical reaction to become part of thecompound as set forth below, are partially or fully fluorinated (orfully or partially deuterated), though such is not necessary as willalso be seen below.

[0036] One example of a method for making the materials of the presentinvention comprises providing a compound R¹ _(4-q)MOR³ _(q) where M isselected from group 14 of the periodic table, OR³ is an alkoxy group, R¹is an alkyl, alkenyl, aryl or alkynyl, and q is from 2 to 4; reactingthe compound R¹ _(4-q)MOR³ _(q) with either a) Mg and R²X² where X² isCl, Br or I and R² is an alkyl, alkenyl, aryl or alkynyl group, or b)reacting with R²X¹ where R² is an alkyl, alkenyl, aryl or alkynyl groupand wherein R2 is fully or partially fluorinated or deuterated and X isan element from group 1 of the periodic table; so as to replace one ofthe OR³ groups in R¹ _(4-q)MOR³ _(q) so as to form R¹ _(4-q)R²MOR³_(q-1).

[0037] The starting material preferably has 1 or 2 (or no) organicgroups (R1) bound to the group 14 element “M”, which organic groups mayor may not comprise fluorine, with the remaining groups bound to M beingalkoxy groups. An additional preferably fluorinated (partially of fully)organic group becomes bound to the group 14 element by one of a numberof reactions. One method (Method A) involves reacting the startingmaterial with magnesium and a compound having the desired organic group(R²) bound to a halogen X² (preferably Cl, Br or I)—namely R² X², whichreaction replaces one of the alkoxy groups with the organic group R². Inthe above example, a single alkoxy group is replaced, however, dependingupon the molar ratios of starting material to R²X² and Mg, more than onealkoxy group can be replaced with an R² organic group. In one example ofthe above, a tetraethoxysilane, MOR³ ₄ is reacted with a compound R²X²where R² is a preferably fluorinated alkyl, aryl, alkenyl or alkynylgroup and X² is preferably Br or I, so as to form R²MOR³ ₃. In anotherexample, R¹MOR³ ₃ is reacted with R²X² so as to form R¹R²MOR³ ₂. Thisgroup of reactions can be referred to as: reacting the starting materialR¹ _(4-q)MOR³ _(q) with R²X² where R² is a preferably fluorinated alkyl,aryl, alkenyl or alkynyl group and X² is preferably Br or I, so as toform R¹ _(4-q)R²MOR³ _(q-1).

[0038] This method A can be described as a method comprising reacting acompound of the general formula R¹ _(4-m)MOR³ _(m), wherein m is aninteger from 2 to 4, OR³ is an alkoxy, and M is an element selected fromgroup 14 of the periodic table; with a compound of the general formulaR²X²+Mg, wherein X² is Br or I, where R¹ and R² are independentlyselected from alkyl, alkenyl, aryl or alkynyl, and wherein at least oneof R¹ and R² is partially or fully fluorinated, so as to make a compoundof the general formula R²MR¹ _(3-n),OR³ _(n.) wherein n is an integerfrom 1 to 3.

[0039] An alternate to the above method (Method B) is to react the samestarting materials (R¹ _(4-q)MOR³ _(q)) with a compound R²X¹ where, asabove, R is an alkyl, alkenyl, aryl or alkynyl group and wherein R² isfully or partially fluorinated or deuterated and X¹ is an element fromgroup I of the periodic table; so as to replace an OR³ group in R¹_(4-q)MOR³ _(q) to form R¹ _(4-q)R²MOR³ _(q-1). In this example, X¹ isan element from group 1 of the periodic table, and is preferably Na, Lior K (more preferably Na or Li). In one example of the above, atetraethoxysilane, MOR³ ₄ is reacted with a compound R²X¹ where R² is apreferably fluorinated alkyl, aryl, alkenyl or alkynyl group and X¹ ispreferably an element from group I of the periodic table, so as to formR²MOR³ ₃. In another example, R¹MOR³ ₃ is reacted with R²X¹ so as toform R1R²MOR³ ₂.

[0040] This method B can be described as a method comprising reacting acompound of the general formula R1_(4-m)MOR3_(m) wherein m is an integerfrom 2 to 4, R1 is selected from alkyl, alkenyl, aryl, or alkyl, alkenylor aryl, and wherein R1 is nonfluorinated, or fully or partiallyfluorinated, OR3 is alkoxy, and M is an element selected from group 14of the periodic table; with a compound of the general formula R2M1,wherein R2 is selected from alkyl, alkenyl, aryl, alkynyl, and whereinR2 is at least partially fluorinated; and M1 is an element from group Iof the periodic table; so as to make a compound of the general formulaR1_(4-m)MOR3_(m-1)R2.

[0041] A modification (Method C) of the aforementioned (Method B), is toreact the starting material (R¹ _(4-q)MOR³ _(q)) with a halogen orhalogen compound so as to replace one or more of the OR³ groups with ahalogen group due to reaction with the halogen or halogen compound. Thehalogen or halogen compound can be any suitable material such ashydrobromic acid, thionylbromide, hydrochloric acid, chlorine, bromine,thionylchloride or sulfurylchloride and the like. Depending upon theratio of halogen or halogen compound to starting material (and otherparameters such as reaction time and/or temperature), one or more alkoxygroups can be replaced by a halogen group—though in most examples, asingle alkoxy group or all alkoxy groups will be replaced. If a singlealkoxy group is replaced, then the starting material R¹ _(4-q)MOR³ _(q)becomes R¹ _(4-q)MOR³ _(q-1)X³ where X³ is a halogen from the halogen orhalogen compound reacted with the starting material (or simply beginwith starting material R¹ _(4-q)MOR³ _(q-1)X³). If all alkoxy groups arereplaced due to the reaction with the halogen or halogen compound, thenthe starting material R¹ _(4-q)MOR³ becomes R¹ _(4-q)MX³ _(q). Then, asmentioned for Method B above, either starting material R¹ _(4-q)MOR³_(q-1)X³ or R¹ _(4-q)MX³ _(q) is reacted with a compound R²X¹ _(where R)² is a preferably fluorinated alkyl, aryl, alkenyl or alkynyl group andX¹ is preferably an element from group I of the periodic table, so as toform R¹ _(4-q)R²MOR³ _(q-1), R¹ _(4-q)R²MX³ _(q-1) (or even R¹ _(4-q)R²₂ MX³ _(q-2) depending upon reaction conditions). A reaction with R¹_(4-q)MOR³ _(q-1)X³ is preferred due to greater ease of control of thereaction.

[0042] This Method C can be described as a method comprising reacting acompound of the general formula X3MOR3₃, where X3 is a halogen, M is anelement selected from group 14 of the periodic table, and OR3 is alkoxy;with a compound of the general formula R1M1; where R1 is selected fromalkyl, alkenyl, aryl and alkynyl and wherein R1 is partially or fullyfluorinated; and Ml is an element from group I of the periodic table; soas to form a compound of the general formula R1MOR3₃.

[0043] Related Methods B and C can be described as a single methodcomprising reacting a compound of the general formula R¹_(4-m)MOR3_(m-n)X_(n) wherein m is an integer from 2 to 4, and n is aninteger from 0 to 2, R1 is selected from alkyl, alkenyl, aryl, or alkyl,alkenyl or aryl, and wherein R1 is nonfluorinated, or fully or partiallyfluorinated;

[0044] OR3 is alkoxy, and M is an element selected from group 14 of theperiodic table; with a compound of the general formula R2M I, wherein R2is selected from alkyl, alkenyl, aryl, alkynyl, and wherein R2 is atleast partially fluorinated, and M1 is an element from group I of theperiodic table; so as to make a compound of the general formulaR2MR1_(4-m)OR3_(m-n)X_(n-1).

[0045] Of course, as will be seen below, the above starting materials inthe method examples set forth above are only examples, as many otherstarting materials could be used. For example, the starting materialcould be a halide rather than an alkoxide (e.g. a mono-, di- ortrichlorosilanes) or another material having both alkoxy and halogengroups on the group 14 element, along with 0, 1 or even 2 organic groups(alkyl, alkenyl, aryl, alkynyl) also bound to the group 14 element.Though the methods for making the materials of the invention preferablyuse starting materials having the group 14 element set forth above, manydifferent combinations of alkoxy groups, halogen groups, and organicgroups (alkyl, alkenyl, . . . etc.) can be bound to the group 14element. And, of course, such starting materials can be commerciallyavailable starting materials or can be made from other availablestarting materials (in which case such materials are intermediatecompounds in the methods for making the materials of the invention).

[0046] In addition, the methods for making the materials of theinvention include, a method for forming a final compound could includeMethods A, B and/or C above. For example, one organic group, preferablyfluorinated, could become bound to the group 14 element M by Method Afollowed by binding a second organic group, preferably fluorinated, tothe group 14 element M by Method B. Or, Method B could be performedfirst, followed by Method A—or Method C could be performed incombination with Methods A and/or B, etc. And, of course, any particularreaction (binding of an organic group to M) could be performed only onceby a particular reaction, or multiple times (binding of multiple organicgroups, the same or different from each other) by repeating the samereaction (a, b or c) multiple times. Many combinations of these variousreactions and starting materials are possible. Furthermore, any of themethods or method combinations could include any of a number ofadditional steps including preparation of the starting material,replacing one or more alkoxy groups of the final compound with halogens,purifying the final compound, hydrolysis and condensation of the finalcompound (as will be described further below), etc.

EXAMPLE 1 Making a Compound I via Method B

CF₂═CF—Cl+sec/tert-BuLi→CF₂═CF—Li+BuCl

CF₂═CF—Li+Si(OEt)₄→CF₂═CF—Si(OEt)₃+EtOLi

[0047] 200 ml of freshly distilled dry Et₂O is added to a 500 ml vessel(under an argon atmosphere). The vessel is cooled down to −80° C. and 15g (0.129 mol) of CF₂═CFCl gas is bubbled to Et₂O. 100 ml (0.13 mol) ofsec-BuLi is added dropwise during three hours. The temperature of thesolution is kept below −60° C. all the time. The solution is stirred for15 minutes and 29 ml (27.08 g, 0.130 mol) of Si(OEt)₄ is added in smallportions. The solution is stirred for over night allowing it to warm upto room temperature. Formed red solution is filtered and evaporated todryness to result crude trifluorovinyltriethoxysilane, CF₂═CFSi(OEt)₃.

EXAMPLE 2 Making a Compound I via Method C

CF₂═CF—Li+ClSi(OEt)₃→CF₂═CF—Si(OEt)₃+LiCl

[0048] CF₂═CFSi(OEt)₃ is also formed when 30.80 g (0.155 mol) ClSi(OEt)₃in Et₂O is slowly added to solution of CF₂═CF—Li (0.155 mol, 13.633 g,prepared in situ) in Et2O at −78° C. Reaction mixture is stirredovernight allowing it slowly warm to room temperature. LiCl is removedby filtration and solution evaporated to dryness to result yellowliquid, crude trifluorovinyltriethoxysilane.

EXAMPLE 3 Making a Compound IV via Method B or C

[0049] Follow steps in Example 1 or 2 above, followed by

CF₂═CF—Si(OEt)₃+excess SOCl₂+py.HCl→CF₂═CF—SiCl₃+3 SO₂+3EtCl

[0050] 24.4 g (0.100 mol) crude trifluorovinyltriethoxysilane, 44 mL(0.60 mol, 71.4 g) thionylchloride and 1.1 g (0.0045 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂ isevaporated and trifluorovinyltrichlorosilane is purified bydistillation.

EXAMPLE 4 Making a Compound I via Method A

C₇F₇Br+Mg+excess Si(OEt)₄→C₇F₇Si(OEt)₃

[0051] 250 g (0.8418 mol) heptafluorobromotoluene, 22.69 g (0.933 mol)magnesium powder, small amount of iodine (15 crystals) and 750 mL(3.3672 mol, 701.49 g) tetraethoxysilane are mixed together at roomtemperature and diethylether is added dropwise to the vigorously stirredsolution until an exothermic reaction is observed (˜250 mL). Afterstirring at room temperature for 16 h diethylether is evaporated. Anexcess of n-heptane (˜600 mL) is added to precipitate the magnesiumsalts. Solution is filtrated and evaporated to dryness. The residue isfractionally distilled under reduced pressure to yieldheptafluorotoluene-triethoxysilane.

EXAMPLE 5 Making a Compound IV via Method A

[0052] Follow the steps in Example 4, followed by

C₇F₇Si(OEt)₃+6 SOCl₂+py.HCl→C₇F₇SiCl₃  2.

[0053] where 114.1 g (0.300 mol) heptafluorotoluenetriethoxysilane, 131mL (1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol)pyridinium hydrochloride are refluxed and stirred for 16 h. Excess ofSOCl₂ is evaporated and perfluorotoluenetrichlorosilane

[0054] isolated by vacuum-distillation.

EXAMPLE 6 Making a Compound III via Method A

[0055] Follow same steps as in Example 5, except isolate (by vacuumdistillation at the end), perfluorotoluenedichloroethoxysilane,CF₃—C₆F₄—Si(OEt)Cl₂

EXAMPLE 7 Making a Compound V from a Compound I or II via Method C

C₆F₅Si(OEt)₃+SOCl₂+py.HCl→C₆F₅Si(OEt)₂Cl+EtCl  1.

C₆F₅Si(OEt)₂Cl+CF₂═CFLi→C₆F₅(CF₂═CF)Si(OEt)₂  2.

C₆F₅(CF₂═CF)Si(OEt)₂+excess SOCl₂+py.HCl→C₆F₅(CF₂═CF)SiCl₂  3.

[0056] 152.0 g (0.460 mol) pentafluorophenyltriethoxysilane, 34 mL(0.460 mol, 54.724 g) thionylchloride and 6.910 g (0.0598 mol)pyridinium hydrochloride are refluxed and stirred for 18 h. Pyridiniumhydrochloride is precipitated at −78° C. and the solution is filtrated.Pentafluorophenylchlorodiethoxysilane

[0057] is isolated by vacuum distillation.

[0058] Then 49.712 g (0.155 mol) pentafluorophenylchlorodiethoxysilane,C₆F₅SiCl(OEt)₂, in Et₂O is slowly added to solution of CF₂═CF—Li (0.155mol, 13.633 g, prepared in situ) in Et₂O at −78° C. Reaction mixture isstirred overnight while it will slowly warm to room temperature. LiCl isremoved by filtration and the product,pentafluorophenlyltrifluorovinyldiethloxysilane,

[0059] purified by distillation.

EXAMPLE 8 Making a Compound VII from a Compound I or II via Method C

[0060] Follow the steps above for Example 7, and then

[0061] 12.1 g (0.0328 mol)pentafluorophenyltrifluorovinyldiethoxysilane, 12 mL (0.1638 mol, 19.487g) thionylchloride and 0.50 g (0.0043 mol) pyridinium hydrochloride arerefluxed and stirred for 24 h. Excess of SOCl₂ is evaporated and residueis fractionally distilled under reduced pressure to yield a mixture of80% pentafluorophenyltrifluorovinyldichlorosilane.

EXAMPLE 9 Making a Compound I via Method A

C₆F₅Br+Mg+2 Ge(OEt)₄<C₆F₅Ge(OEt)₃

[0062] 61.5 mL (0.4944 mol, 122.095 g) pentafluorobromobenzene, 13.22 g(0.5438 mol) magnesium powder and 250.00 g (0.9888 mol)tetraethoxygermane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜400 mL). After stirring at 35° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜400 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldpentafluorophenyl-triethoxygermane.

EXAMPLE 10 Making a Compound IV via Method A

[0063] Follow the steps in Example 9, then:

[0064] 50 g (0.133 mol) pentafluorophenyltriethoxygermane, 58 mL (0.80mol, 95.2 g) thionylchloride and 1.97 g (0.017 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂ isevaporated and pentafluorophenyltrichlorogermane isolated by vacuumdistillation.

EXAMPLE 11 Making a Compound I via Method A

Cl₁₀F₇Br+Mg+excess Si(OEt)₄→C₁₀F₇Si(OEt)₃

[0065] 166.5 g (0.50 mol) 2-bromoperfluoronaphthalene, 13.37 g (0.55mol) magnesium powder and 448.0 mL (2.00 mol, 416.659 g)tetraethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜200 mL). After stirring at 35° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜400 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldperfluoronaphthalenetriethoxysilane.

EXAMPLE 12 Making a Compound IV via Method A

[0066] Follow the steps in Example 11, then

[0067] 100 g (0.240 mol) perfluoronaphthalenetriethoxysilane, 105.2 mL(1.442 mol, 171.55 g) thionylchloride and 3.54 g (0.0306 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂ isevaporated and perfluoronaphthalenetrichlorosilane isolated by vacuumdistillation.

EXAMPLE 13 Making Compound V via Method A

C₆F₅Br+Mg+4MeSi(OMe)₃→C₆F₅(Me)Si(OMe)₂

[0068] 57.9 mL (0.465 mol, 114.726 g) bromopentafluorobenzene, 12.42 g(0.511 mol) magnesium powder and 265 mL (1.858 mol, 253.128 g)methyltrimethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜320 mL). After stirring at 45° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜300 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue, methyl(pentafluorophenyl)dimethoxysilane, is used withoutfurther purification.

EXAMPLE 14 Making Compound VII via Method A

[0069] Follow steps in Example 13, then

[0070] 81.68 g (0.300 mol) methyl(pentafluorophenyl)dimethoxysilane, 109mL (1.50 mol, 178.4 g) thionylchloride and 3.69 g (0.0319 mol)pyridinium hydrochloride are refluxed and stirred for 16 h. Excess ofSOCl₂ is evaporated and methyl(pentafluorophenyl)dichlorosilane isolatedby vacuum-distillation.

EXAMPLE 15 Making a Compound V via Method A

2C₆F₅Br+2Mg+Si(OEt)₄→(C₆F₅)₂Si(OEt)₂

[0071] 265.2 mL (1.95 mol, 525.353 g) bromopentafluorobenzene, 52.11 g(2.144 mol) magnesium powder and 216 mL (0.975 mol, 203.025 g)tetraethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜240 mL). The solution is stirredfor 30 minutes after which additional 90 nil of Et₂O is carefully added.After stirring at 35° C. for 16 h the mixture is cooled to roomtemperature and diethylether evaporated. An excess of n-heptane (˜600mL) is added to precipitate the magnesium salts. Solution is filtratedand evaporated to dryness. The residue is fractionally distilled underreduced pressure to yield di(pentafluorophenyl)diethoxysilane.

EXAMPLE 16 Making a Compound V via Method C

C₆F₅Cl+sec-BuLi→C₆F₅Li+sec-BuCl

C₆F₅Li+C₆F₅Si(OEt)₂Cl→(C₆F₅)₂Si(OEt)₂+LiCl

[0072] 39.52 g (0.195 mol) chloropentafluorobenzene is weighed to a 1000mL vessel and 250 mL Et₂O is added. The vessel is cooled down to −70° C.and 150 mL (0.195 mol) of sec-BuLi (1.3 M) is added dropwise during onehour. The temperature of the solution is kept below −50° C. all thetime. The solution is stirred for 30 minutes and 62.54 g (0.195 mol) ofdiethoxychloropentafluorophenylsilane in Et₂O (100 mL) is added in smallportions. The solution is stirred for over night allowing it to warm upto room temperature. Formed clear solution is filtered and evaporated todryness to result di(pentafluorophenyl)diethoxysilane, (C₆F₅)₂Si(OEt)₂.

EXAMPLE 17 Making a Compound VII via Method A or C

[0073] Follow the steps in Example 15 or Example 16, then:

(C₆F₅)₂Si(OEt)₂+SOCl₂+py.HCl→(C₆F₅)₂SiCl₂

[0074] 180.93 g (0.400 mol) di(pentafluorophenyl)diethoxysilane, 146 mL(2.00 mol, 237.9 g) thionylchloride and 4.92 g (0.0426 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Excess of SOCl₂ isevaporated and di(pentafluorophenyl)dichlorosilane isolated byvacuum-distillation.

EXAMPLE 18 Making an “Other Compound” via Method A

C₆F₅MgBr+HSiCl₃→C₆F₅(H)SiCl₂

[0075] 600.0 mL (0.300 mol) pentafluorophenyl magnesiumbromide (0.5 Msol. in Et₂O) is added dropwise to a solution of 30.3 mL (0.300 mol,40.635 g) HSiCI₃ in Et₂O at −70° C. Reaction mixture is allowed to warmslowly to room temperature by stirring overnight. Diethylether isevaporated and an excess of n-heptane (˜200 mL) is added to precipitatethe magnesium salts. Solution is filtrated and evaporated to dryness.The residue, pentafluorophenyldichlorosilane, is purified by fractionaldistillation.

EXAMPLE 19 Making a Compound I via Method C

CH≡C—Na+ClSi(OEt)₃<CH≡C—Si(OEt)₃+NaCl

[0076] 79.49 g (0.400 mol) ClSi(OEt)₃ μl Et₂O is slowly added to aslurry of CH≡C—Na (0.400 mol, 19.208 g) in Xylene/light mineral oil at−78° C. Reaction mixture is stirred overnight allowing it slowly warm toroom temperature. NaCl is removed by filtration and solution evaporatedto dryness to result acetylenetriethoxysilane.

EXAMPLE 20 Making a Compound VII via Method A

C₆F₅Br+Mg+CH₂═CH—Si(OEt)₃→C₆F₅(C₂—CH)Si(OEt)₂  1.

C₆F₅(CH₂═CH)Si(OEt)₂+SOCl₂+py.HCl→C₆F₅(CH₂═CH)SiCl₂  2.

[0077] 100 mL (0.8021 mol, 198.088 g) pentafluorobromobenzene, 24.90 g(1.024 mol) magnesium powder and 670 mL (3.2084 mol, 610.623 g)vinyltriethoxysilane are mixed together at room temperature and Et₂O isadded dropwise to the vigorously stirred solution until an exothermicreaction is observed (˜400 mL). After stirring at 35° C. for 16 h themixture is cooled to room temperature and diethylether evaporated. Anexcess of n-heptane (˜500 mL) is added to precipitate the magnesiumsalts. Solution is filtrated and evaporated to dryness. The residue isfractionally distilled under reduced pressure to yieldpentafluorophenylvinyldiethoxysilaiie.

[0078] 120.275 g (0.3914 mol) pentafluorophenylvinyldiethoxysilane, 143mL (1.9571 mol, 232.833 g) thionylcliloride and 5.880 g (0.0509 mol)pyridinium hydrochloride are refluxed and stirred for 24 h. Excess ofSOCl₂ is evaporated and pentafluorophenylvinyldichlorosilane isolated byvacuum distillation.

EXAMPLE 21 Making a Compound I from Method B

ClSi(OEt)₃→CH₂═CH—C(═O)—O—Si(OEt)₃+NaCl

[0079] 6.123 g (0.0651 mol) sodium acrylate is dissolved to 25 mL THFand cooled to −70° C. 12.8 mL (0.0651 mol, 12.938 g)chlorotriethoxysilane in THF (15 mL) is added dropwise to reactionsolution. The solution is stirred for over night allowing it to warm upto room temperature. NaCl is removed by filtration and solutionevaporated to dryness to result clear liquid, acryltriethoxysilane.

EXAMPLE 22 Making a Compound II

CF₃—(CF₂)₇CH₂—CH₂—Si(OEt)₃+SOCl₂+py.HCl<CF₃—(CF₂)₇—CH₂—CH₂—Si(OEt)₂Cl

[0080] 183.11 g (0.300 mol) 1H,1H,2H,2H-Perfluorodecyltriethoxysilane,22 mL (0.300 mol, 35.69 g) thionylchloride and 4.51 g (0.039 mol)pyridinium hydrochloride are refluxed and stirred for 16 h. Excess ofSOCl₂ is evaporated and 1H,1H,2H,2H-Perfluorodecylchlorodi(ethoxy)silaneisolated by vacuum-distillation.

[0081] Though this example is not using Methods A, B or C, method Ccould be used to add a second organic group (replacing the C1 group), orMethods A and B could be used replace an ethoxy group in the startingmaterial with an additional organic group. Also, the starting materialcould be made by Methods A, B or C (starting earlier with atetraethoxysilane and reacting as in the other examples herein).

EXAMPLE 23 Making a Compound I via Method A

C₈F₁₇Br+Mg+excess Si(OEt)₄→C₈ F₁₇Si(OEt)₃

C₈F₁₇Si(OEt)₃+excess SOCl₂+py.HCl→C₈F₁₇SiCl₃

[0082] 250 g (0.501 mol) 1-Bromoperfluorooctane (or 273.5 g, 0.501 mol1-Iodoperfluorooctane), 13.39 g (0.551 mol) magnesium powder, smallamount of iodine (15 crystals) and 363 mL (2.004 mol, 339.00 g)tetraethoxysilane are mixed together at room temperature anddiethyletlier is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (β200 mL). After stirring at roomtemperature for 16 h diethylether is evaporated. An excess of n-heptane(˜400 mL) is added to precipitate the magnesium salts. Solution isfiltrated and evaporated to dryness. The residue is fractionallydistilled under reduced pressure to yield perfluorooctyltriethoxysilane.

EXAMPLE 24 Making a Compound IV via Method A

[0083] Follow the steps in Example 23, then

[0084] 174.7 g (0.300 mol) perfluorooctyltriethoxysilane, 131 mL (1.800mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Excess of SOCl₂ isevaporated and perfluorooctyltrichlorosilane isolated byvacuum-distillation.

EXAMPLE 25 Making a Compound I via Method A

CF₂═CF—O—CF₂—CF₂—Br+Mg+excess Si(OEt)₄→CF₂═CF—O—CF₂—CF₂—Si(OEt)₃

[0085] 138.47 g (0.500 mol) 2-Bromotetrafluoroethyl trifluorovinylether, 13.37 g (0.550 mol) magnesium powder, small amount of iodine (10crystals) and 362 mL (2.000 mol, 338.33 g) tetraethoxysilane are mixedtogether at room temperature and diethylether is added dropwise to thevigorously stirred solution until an exothermic reaction is observed(˜200 mL). After stirring at room temperature for 16 h diethylether isevaporated. An excess of n-heptane (˜400 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldtetrafluoroethyl trifluorovinyl ether triethoxysilane.

EXAMPLE 26 Making a Compound IV via Method A

[0086] Follow steps in Example 25, followed by

[0087] 108.1 g (0.300 mol) tetrafluoroethyl trifluorovinyl ethertriethoxysilane, 131 mL (1.800 mol, 214.1 g) thionylchloride and 4.51 g(0.039 mol) pyridinium hydrochloride are refluxed and stirred for 16 h.Excess of SOCl₂ is evaporated and tetrafluoroethyl trifluorovinyl ethertrichlorosilane is isolated by vacuum-distillation.

EXAMPLE 27 Making a Compound I via Method B

CF≡C—Li+ClSi(OEt)₃→CF—C—Si(OEt)₃+LiCl

[0088] 30.80 g (0.155 mol) ClSi(OEt)₃ in Et₂O is slowly added tosolution of CF≡C—Li (0.155 mol, 7.744 g, prepared in situ) in Et₂O at−78° C. Reaction mixture is stirred overnight allowing it slowly warm toroom temperature. LiCl is removed by filtration and solution evaporatedto dryness to result fluoroacetylenetriethoxysilane.

EXAMPLE 28 Making a Compound VIII via Method C

(C₆F₅)₂Si(OEt)₂+SOCl₂→(C₆F₅)₂Si(OEt)Cl+EtCl+SO₂

C₆F₅Li+(C₆F₅)₂Si(OEt)Cl→(C₆F₅)₃SiOEt+LiCl

(C₆F₅)₃SiOEt+SOCl₂<(C₆F₅)₃SiCl+EtCl+SO₂

[0089] 180.93 g (0.400 mol) di(pentafluorophenyl)diethoxysilane, 29 mL(0.400 mol, 47.6 g) thionylchloride and 4.92 g (0.0426 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Unreacted SOCl₂ isevaporated and di(pentafluorophenyl)chloroethoxysilane isolated byvacuum distillation.

[0090] 88.54 g (0.200 mol) of di(pentafluorophenyl)chloroethoxysilane inEt₂O is slowly added to solution of C₆F₅—Li (0.200 mol, 34.80 g,prepared in situ) in Et₂O at −78° C. The solution is stirred for overnight allowing it to warm up to room temperature. Formed clear solutionis filtered and evaporated to dryness to resulttri(pentafluorophenyl)ethoxysilane, (C₆F₅)₃SiOEt.

EXAMPLE 28 Making a Compound IX via Method C

[0091] Follow steps in Example 28, followed by

[0092] 114.86 g (0.200 mol) tri(pentafluorophenyl)ethoxysilane, 14.6 mL(0.200 mol, 23.8 g) thionylchloride and 2.46 g (0.0213 mol) pyridiniumhydrochloride are refluxed and stirred for 16 h. Unreacted SOCl₂ isevaporated and tri(pentafluorophenyl)chlorosilane isolated byvacuum-distillation.

[0093] In addition to altering the organic groups in the above examples,it is of course also possible to use other reagents in the methodsabove. For example, in place of diethyl ether, other solvents such asTHF could be used. In place of n-heptane (in Method A) other non polarsolvents such as n-hexane could be used. And in place of thionylchloride (for replacing one or more alkoxy groups with a halogen),chlorine, hydrochloric acid, hydrobromic acid, thionylbromide, chlorineor sulfurylcliloride could be used. Also, the temperatures and times(and other process parameters) can be varied as desired. In one example,it is preferred that the molar ratio of the starting material to R²X¹(Methods B or C) is 0.5:1 to 2:1—preferably 1:1. Also, the startingmaterial and R²X¹ are preferably mixed at a temperature less than −40 Cdegrees, e.g. between −50 C and −100 C and warmed to a highertemperature over a period of four hours or more (this higher temperaturecan be room temperature or higher if desired)—or over a longer period oftime such as overnight.

[0094] As can be seen from the examples above, Methods B and C involvereacting a first compound (having an M group selected from group 14 ofthe periodic table, 0, 1 or 2 organic groups bound to M) with a secondcompound (having an element from group 1 of the periodic table and a“new” organic group). As can also be seen from the above, such areaction can take place if the first compound has alkoxy groups bound toM or both alkoxy and halogen groups (0, 1 or 2 halogen groups) bound toM. Method C, as mentioned earlier, is a variation of Method B—and bothmethods can be viewed as comprising: reacting a compound of the generalformula R¹ _(4-m)MOR³ _(m-n)X_(n), where R¹ is any nonfluorinated(including deuterated) or partially or fully fluorinated organic group(preferably a partially or fully fluorinated aryl, alkenyl, alkynyl oralkyl group) as set forth above, where M is selected from group 14 ofthe periodic table, where X is a halogen, where OR³ is an alkoxy group,where m=2 to 4 and n=0 to 2. R¹ _(4-m)OR³ _(m-n)X_(n) is reacted withR²X¹ where R² is selected from alkyl alkenyl, aryl or alkynyl (and whereR² is fluorinated (fully or partially), and where X¹ is an element fromgroup 1 of the periodic table. X¹ is preferably Na, Li or K, morepreferably Na or Li, and most preferably Li. M is preferably Si, Ge orSn, more preferably Si or Ge, and most preferably Si. X is preferablyCl, Br or I, more preferably Cl or Br, and most preferably Cl. OR³ ispreferably an alkoxy group having from 1 to 4 carbon atoms, morepreferably from 1 to 3 carbons, and most preferably 2 carbons (ethoxy).Also, “m” is preferably 3 or 4, whereas “n” is preferably 0 or 1.

[0095] R¹ and R² are independently preferably partially or fullyfluorinated (though not necessarily as can be seen in prior examples)organic groups such as an aryl group (by aryl group we mean any organicgroup having a ring structure) though preferably a five or six carbonring that is unsubstituted or substituted. For a six carbon ringstructure, 1, 2 or 3 substituents can be bound to the ring, whichsubstituents can be actively bound to the ring via a variation on theMethod C set forth above (to be described further below). Thesubstituents can be alkyl groups of any desired length, straight orbranched chain, preferably fluorinated, and preferably having from 1 to4 carbon atoms. Or the substituents on the ring structure can comprise aC═C double bond and be an alkenyl group (by alkenyl group we mean anyorganic group with a C═C double bond) such as an acrylate, vinyl orallyl group. A fluorinated vinyl, methyl or ethyl group on a fluorinatedphenyl group are examples. Or, the aryl group could be a multi ringstructure (e.g. perfluoronaphthalene or a biphenyl group). Or R1 and R²could independently be an alkenyl group such as a vinyl or longer chaingroup having a C═C double bond, or a group having other types of doublebonds (e.g C═O double bonds or both C═C and C═O double bonds) such asacrylate and methacrylate groups. R¹ and R² could also be an alkynylgroup (by alkynyl group we mean any organic group with a carbon-carbontriple bond) as mentioned previously, as well as an alkyl group. If analkyl group (by alkyl group we mean a carbon chain of any length),preferably the carbon chain is from 1 to 14, and more preferably from 4to 8. Perfluorinated alkyl groups from 1 to 8 carbons can be used, aswell as fluorinated (e.g. partially fluorinated) groups longer than 8carbons. All the organic groups above could be deuterated in stead offluorinated (or partially deuterated and partially fluorinated), thoughfully or partially fluorinated (particularly fully fluorinated) ispreferred.

[0096] In Method C set forth above, an organic (or hybrid) group “R”(e.g. R2) becomes bound to a group 3-6 or 13-16 element “M” by replacinga halogen “X” bound to “M” via the specified reaction. In an alternativeto this method (Method D), an organic (or hybrid) group “R” (e.g. R¹)comprises the halogen “X”—preferably Cl or Br (rather than “X” beingbound to “M”). Thus when the reaction is performed, R2 replaces X boundto R1, such that R2 becomes bound to R1 (which is in turn bound to M).Preferably the other groups bound to M are alkoxy groups (OR3) or otherorganic groups. More particularly, such a method comprises providing acompound X_(a)R¹MOR³ ₂R⁴ where a is from 1 to 3, X is a halogen(s) boundto R¹, R1 is an organic group (preferably an aryl, alkyl, alkenyl oralkynyl—more preferably an alkyl or aryl group), OR³ is an alkoxy, andR⁴ is either an additional alkoxy group or an additional organic group(selected from aryl, alkyl, alkenyl or alkynyl), and reacting thiscompound with R²M¹ where M¹ is selected from group I of the periodictable and R² is an organic group preferably selected from aryl, alkyl,alkenyl and alkynyl, etc., so as to form R² _(a)R¹ _(MOR) ³ ₂R^(4.)

[0097] In one example, R⁴ is an alkoxy group the same as OR³, such thatthe method comprises reacting X_(a)R¹MOR³ ₃ with R²M¹ to form R²,R¹MOR³₃ (where R¹ and OR³ are bound to M and R² is bound to R¹. In anotherexample, R⁴ is an organic group selected from aryl, alkyl, alkenyl andalkynyl. Preferably OR3 is a methoxy, ethoxy or propoxy, R¹ is an arylor alkyl (straight or branched chain) having from 1 to 14 carbons, andR2 is an aryl, alkyl, alkenyl or alkynyl, where a=1 or 2 if R¹ is analkyl and a=1, 2 or 3 if R¹ is an aryl group. R² can be an epoxy,acrylate, methacrylate, vinyl, allyl or other group capable of crosslinking when exposed to an electron beam or in the presence of aphotoinitiator and electromagnetic energy (e.g. UV light).

EXAMPLE A Forming a Compound I or IV via Method D

1,4-Br₂C₆F₄+Mg+Si(OEt)₄→Br(C₆F₄)Si(OEt)₃  1.

Br(C₆F₄)Si(OEt)₃+CF₂═CFLi→(CF₂═CF)(C₆F₄)Si(OEt)₃  2.

[0098] 250 g (0.812 mol) 1,4-dibromotetrafluorobenzene, 21.709 g (0.8932mol) magnesium powder, small amount of iodine (15 crystals) and 181 mL(0.812 mol, 169.164 g) tetraethoxysilane were mixed together at roomtemperature and diethylether was added dropwise to the vigorouslystirred solution until an exothermic reaction was observed (˜250 mL).After stirring at room temperature for 16 h diethylether was evaporated.An excess of n-heptane (˜600 mL) was added to precipitate the magnesiumsalts. Solution was filtrated and evaporated to dryness. The residue wasfractionally distilled under reduced pressure to yield4-bromotetrafluorophenyltriethoxysilane.

[0099] 78.246 g (0.200 mol) 4-bromotetrafluorophenyltriethoxysilane inEt₂O is slowly added to solution of CF₂═CF—Li (0.200 mol, 17.592 g,prepared in situ) in Et₂O at −78° C. Reaction mixture is stirredovernight while it will slowly warm to room temperature. LiBr is removedby filtration and the product, 4-triethoxysilyl-perfluorostyrene,purified by distillation.

[0100] 117.704 g (0.300 mol) 4-triethoxysilylpertluorostyrene, 131 mL(1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride were refluxed and stirred for 16 h. Excess of SOCl₂ wasevaporated and 4-trichlorosilyl-perfluorostyrene isolated byvacuum-distillation.

[0101] The above example could be modified where 2 or 3 halogens (inthis case Br) are bound to the phenyl group so as to result in multiplevinyl substituents. Also, the phenyl group could be another organicgroup such as an straight or branched chain alkyl group, a multi ringaryl group, etc., whereas the vinyl group could be any suitable organicgroup capable of binding to a group I element (in the above example Li)and replacing the halogen (in the above example Br). Examples other thanvinyl include methyl, ethyl, propyl, phenyl, epoxy and acrylate.

EXAMPLE B Forming a Compound I via Method D

CF₂Cl—C(═O)—ONa+ClSi(OEt)₃→CF₂Cl—C(═O)—O—Si(OEt)₃+NaCl

CF₂═CF—Li+CF₂Cl—C(═O)—O—Si(OEt)₃→CF₂—CF—CF₂—C(═O)—O—Si(OEt)₃+LiCl

[0102] 15.246 g (0.10 mol) sodium chlorodifluoroacetate, is dissolved to100 mL Et₂O and cooled to −70° C. 19.7 mL (0.10 mol, 19.872 g)chlorotriethoxysilane in Et₂O (50 mL) was added dropwise to reactionsolution. The solution was stirred for over night allowing it to warm upto room temperature. NaCl is removed by filtration and solutionevaporated to dryness to result clear colourless liquid,chlorodifluoroacetic acid, triethoxysilyl ester.

[0103] 29.27 g (0.10 mol) chlorodifluoroacetic acid, triethoxysilylester, is dissolved to 100 mL Et₂O and slowly added to solution ofCF₂═CF—Li (0.10 mol, 8.796 g, prepared in situ) in Et₂O at −78° C.Reaction mixture is stirred overnight allowing it slowly warm to roomtemperature. LiCl is removed by filtration and solution evaporated todryness to result yellow liquid, crude perfluoro-3-butene acid,triethoxysilyl ester.

EXAMPLE C Forming a Compound I or IV via Method D

Br(C₆F₄)Si(OEt)₃+C₆F₅—Li→C₆F₅—C₆F₄—Si(OEt)₃+LiBr

[0104] 78.246 g (0.200 mol) 4-bromotetrafluorophenyltriethoxysilane inEt₂O is slowly added to solution of C₆F₅—Li (0.200 mmol, 34.80 g,prepared in situ) in Et₂O at −78° C. Reaction mixture is stirredovernight while it will slowly warm to room temperature. LiBr is removedby filtration and the product, perfluorobiphenyltriethoxysilane,purified by distillation.

[0105] 143.516 g (0.300 mol) perfluorobiphenyltriethoxysilane, 131 mL(1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride were refluxed and stirred for 16 h. Excess of SOCl₂ wasevaporated and perfluorobiphenyltrichlorosilane isolated byvacuum-distillation.

EXAMPLE D Forming a Compound I or IV via Method D

1,4-Br₂C₄F₈+Mg+Si(OEt)₄ Br(CF₂)₄Si(OEt)₃

Br(CF₂)₄Si(OEt)₃+CF₂═CFLi→CF₂═CF—(CF₂)₄→Si(OEt)₃

[0106] 143.94 g (0.40 mol) 1,4-dibromooctafluorobutane, 10.69 g (0.44mol) magnesium powder, small amount of iodine (15 crystals) and 88 mL(0.40 mol, 82.42 g) tetraethoxysilane were mixed together at roomtemperature and diethylether was added dropwise to the vigorouslystirred solution until an exothermic reaction was observed (˜200 mL).After stirring at room temperature for 16 h diethylether was evaporated.An excess of n-heptane (˜400 mL) was added to precipitate the magnesiumsalts. Solution was filtrated and evaporated to dryness. The residue wasfractionally distilled under reduced pressure to yield4-bromooctafluorobutanetriethoxysilane.

[0107] 88.641 g (0.200 mol) 4-bromooctafluorobutanetriethoxysilane inEt₂O is slowly added to solution of CF₂═CF—Li (0.200 mol, 17.592 g,prepared in situ) in Et₂O at −78° C. Reaction mixture is stirredovernight while it will slowly warm to room temperature. LiBr is removedby filtration and the product, perfluoro-1-hexenetriethoxysilane,purified by distillation.

[0108] 133.295 g (0.300 mol) perfluoro-1-hexenetriethoxysilane, 131 mL(1.800 mol, 214.1 g) thionylchloride and 4.51 g (0.039 mol) pyridiniumhydrochloride were refluxed and stirred for 16 h. Excess of SOCl₂ wasevaporated and perfluoro-1-hexenetrichlorosilane isolated byvacuum-distillation.

[0109] In the above “Method D” examples, R¹, R², R³ and R⁴ arepreferably partially or fully fluorinated.

[0110] Hydrolysis and Condensation of the Compound(s):

[0111] Compounds IV, VII and IX have organic (or hybrid) R group(s) andhalogen(s) (preferably Br or Cl) bound to M (selected from groups 3-6 or13-16—preferably group 14)). These compounds can be hydrolyzed alone orin any combination to result in a material having a -M-O-M-O— backbonewith R groups bound to the backbone, and that preferably has a molecularweight of from 500 to 10,000 (more preferably from 500 to 5000). In oneexample, a compound selected from Compound IV is hydrolyzed with anothercompound selected from Compound IV. In another example, a singlecompound from Compound VII is hydrolyzed. Many other combinations arepossible, including: a) Compound IV+Compound VII; b) CompoundIV+Compound IV+Compound IV; c) Compound VII+Compound VII; d) CompoundIV+Compound VII+Compound IX; e) Compound IV+Compound IV+Compound IX; f)Compound VII+Compound IX, etc. Any other combinations, in any desiredratio, can be used for the hydrolysis and eventual deposition.

[0112] The hydrolysis/condensation procedure can comprise fivesequential stages: Dissolvement, hydrolysis and co-condensation,neutralization, condensation and stabilization. Not all stages arenecessary in all cases. In the hydrolysis, chlorine atoms are replacedwith hydroxyl groups in the silane molecule. The following descriptiontakes as an example compounds that have chlorine as the halogen thattakes part in the hydrolysis reaction, and silicon is the metal in thecompound. Hydrochloric acid formed in the hydrolysis is removed in theneutralization stage. Silanols formed in the hydrolysis are attachedtogether for a suitable oligomer in the condensation stage. The oligomerformed in the condensation are stabilized in the end. Each stage can bedone with several different ways.

EXAMPLE I

[0113] Dissolvement. Chlorosilanes are mixed together in an appropriatereaction container and the mixture is dissolved into a suitable solventlike tetrahydrofuran. Instead of tetrahydrofuran, other solvents can beused (pure or as a mixture): acetone, chloroform, diethyl ether, ethylacetate, methyl-isobutyl ketone, methyl ethyl ketone, acetonitrile,ethylene glycol dimethyl ether, triethylamine, formic acid,nitromethane, 1,4-dioxan, pyridine, acetic acid.

[0114] Hydrolysis. The reaction mixture is cooled to 0° C. Thehydrolysis is performed by adding water (H₂O) into the reaction mixture.The water is added in 1:4 (volume/volume)water-tetrahydrofuran-solution. Water is used equimolar amount as thereare chlorine atoms in the starting reagents. The reaction mixture isheld at 0° C. temperature during the addition. The reaction mixture isstirred at room temperature for 1 hour after addition. Instead oftetrahydrofuran, water can be dissolved into pure or mixture offollowing solvents: acetone, chloroform diethyl ether, ethyl acetate,methyl-isobutyl ketone, methyl ethyl ketone, acetonitrile, ethyleneglycol dimethyl ether, triethylamine, formic acid, nitromethane,1,4-dioxan, pyridine, acetic acid. In the place of water (H₂O) can beused: deuterium oxide (D₂O) or HDO. A part of the water can be replacedwith alcohols, deuterium alcohols, fluorinated alcohols, chlorinatedalcohols, fluorinated deuterated alcohols, and/or chlorinated deuteratedalcohols. The reaction mixture may be adjusted to any appropriatetemperature. Excess of water can be used. Some level co-condensation canhappen during the hydrolysis that can be seen as increment of materialmolecular mass.

[0115] Neutralization. The reaction mixture is neutralized with puresodium hydrogen carbonate. NaHCO₃ is added into cooled reaction mixtureat 0° C. temperature (NaHCO₃ is added equimolar amount as there ishydrochloric acid in the reaction mixture). The mixture is stirred atthe room temperature for a while. After the pH of the reaction mixturehas reached value 7, the mixture is filtered. The solvent is thenevaporated with rotary evaporator (p=250-50 mbar, t(bath)=+30° C.).

[0116] Instead of NaHCO₃ can be used pure potassium hydrogen carbonate(KHCO₃), sodium carbonate (Na₂CO₃), potassium carbonate (K₂CO₃), sodiumhydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide(Ca(OH)₂), magnesium hydroxide (Mg(OH)₂) ammonia (NH₃), trialkylamines(R₃N, where R is hydrogen or straight/branched chain C_(x)H_(y), x<10,for example triethanolamine), trialkyl ammonium hydroxides (R₃NOH, R₃N,where R is hydrogen or straight/branched chain C_(x)H_(y), x<10). Allneutralization reagents can be added into the reaction mixture also as asolution of any appropriate solvent. Neutralization can be performedalso with solvent-solvent extraction or with azeotropic waterevaporation.

[0117] Procedure for solvent-solvent-extraction: The solvent isevaporated off after the hydrolysis. The material is dissolved into pureor mixture of solvents such as: chloroform, ethyl acetate, diethylether, di-isopropyl ether, dichloromethane, methyl-isobutyl ketone,toluene, carbon disulphide, carbon tetrachloride, benzene, nitromethane,mehylcyclohexane, or chlorobenzene. The solution is extracted severaltimes with water or D₂O until the pH of the organic layer is over value6. The solvent is then evaporated with rotary evaporator (p=250-50 mbar,t(bath)=+30° C.).

[0118] Procedure for azeotropic water evaporation: The solvent isevaporated off after the hydrolysis. The material is dissolved intomixture of water and one of the following solvents (1:10 volume/volume):tetrahydrofuran, ethanol, acetonitrile, 2-propanol, tert-butanol,ethylene glycol dimethyl ether, triethylamine, 2-propanol. The formedsolution is evaporated to dryness. The material is dissolved again intothe same mixture of water and the solvent. Evaporation and additioncycle is repeated until pH value of the material solution is 7. Thesolvent is then evaporated with rotary evaporator (p=250-50 mbar,t(bath)=+30° C.).

[0119] Neutralization stage in cases where condensation stage is passed:In the neutralization stage evaporation of the solvent in the end is notnecessary always. In these cases this stage is aborted after filtering(the reaction mixture is neutral) and the synthesis is continued instabilization stage (the condensation stage is passed).

[0120] Condensation. The material is stirred with magnetic stirrer barunder 12 mbar pressure for few hours. Water, which forms during thisfinal condensation, evaporates off. The pressure in this stage can be ina large range. The material can be heated while vacuum treatment. Insome cases this stage is not necessary.

[0121] Stabilization. The material is dissolved into cyclohexanone,which is added 30 weight-% of the materials weight. The pH of thesolution is adjusted to value 2,0 with acetic acid. In the place ofcyclohexanone can be used any of a number of other solvents, (alone oras a mixture), such as methyl-isobutyl ketone, 2-propanol, ethanol,methanol, 1-propanol, tetrahydrofuran, acetone, nitromethane,chlorobenzene, dibutyl ether, mesitylene, 1,1,2,2-tetrachloroethane,tricliloroethanes, ethyl lactate, 1,2-propanediol monomethyl etheracetate and/or carbon tetrachloride. In the place of acetic acid can beused regular or deuterated forms of following acids, among others:formic acid, propanoic acid, monofluoro acetic acid, trifluoro aceticacid, trichloro acetic acid, dichloro acetic acid and/or monobromoacetic acid.

[0122] Stabilization in cases when the condensation stage is bypassed:Acetic acid is added into the mixture until a pH value of 3-4 isreached. The solution is evaporated until appropriate concentration ofthe oligomer in the solution has reached (about 50 w-% oligomer, 49 w-%solvent and 1 w-% acid, “solvent” is the solvent of the dissolvement andhydrolysis stages).

[0123] In Example I above, “chlorosilanes” are initially mixed togetherwith tetrahydrofuran. As mentioned earlier, this can be an almostunlimited number and type of compounds as disclosed ill detail earlierherein—including a large number of chlorosilanes and otherhalo-metal-organic compounds in accordance with the invention and inaccordance with the ultimate properties desired in the final material.If one of the compounds to be hydrolyzed and condensed ispentafluorophenyltrichlorosilane, this can be prepared as in the methodsset forth above, by:

C₆F₅Br+Mg+excess Si(OEt)₄→C₆F₅Si(OEt)₃+(C₆F₅)₂Si(OEt)₂

C₆F₅Si(OEt)₃+SOCl₂+py.HCl→C₆F₅SiCl₃

[0124] 100 mL (0.8021 mol, 198.088 g) pentafluorobromobenzene, 24.90 g(1.024 mol) magnesium powder and 716 mL (3.2084 mol, 668.403 g)tetraethoxysilane are mixed together at room temperature anddiethylether is added dropwise to the vigorously stirred solution untilan exothermic reaction is observed (˜200 mL). After stirring at 35° C.for 16 h the mixture is cooled to room temperature and diethyletherevaporated. An excess of n-heptane (˜500 mL) is added to precipitate themagnesium salts. Solution is filtrated and evaporated to dryness. Theresidue is fractionally distilled under reduced pressure to yieldpentafluorophenyltriethoxysilane.

[0125] 100 mL (0.375 mol, 124.0 g) pentafluorophenyltriethoxysilane, 167mL (2.29 mol, 272.0 g) thionylchloride and 5.63 g (0.0487 mol)pyridinium hydrochloride are refluxed and stirred for 24 h. Excess ofSOCl₂ is evaporated and pentafluorophenyltrichlorosilane

[0126] isolated by vacuum-distillation.

[0127] If a second of the compounds to be hydrolyzed and condensed istrifluorovinyltrichlorosilane, this can be prepared by:

[0128] 119 mL (0.155 mol) sec-butyllithium (1.3 M solution incyclohexane) is added under argon with stirring to 18.053 g (0.155 mol)chlorotrifluoroethylene

[0129] dissolved in Et₂O at −80° C. After the addition is complete thereaction mixture is stirred for 15 min to yieldlithiumtrifluoroethylene.

[0130] 30.80 g (0.155 mol) ClSi(OEt)₃ in Et₂O is slowly added tosolution of CF₂═CF—Li (0.155 mol, 13.633 g, prepared in situ) in Et₂O at−78° C. Reaction mixture is stirred overnight while it will slowly warmto room temperature. LiCl is removed by filtration and the product,trifluorovinyltriethoxysilane,

[0131] is isolated by distillation.

[0132] 24.4 g (0.100 mol) trifluorovinyltriethoxysilane, 44 mL (0.60mol, 71.4 g) thionylchloride and 0.497 g (0.0045 mol) pyridiniumhydrochloride are refluxed and stirred for 24 h. Excess of SOCl₂ isevaporated and trifluorovinyltrichlorosilane

[0133] is purified by distillation.

[0134] Then, to a solution of trifluorovinyltrichlorosilane andpentafluorophenyltrichlorosilane at a molar ratio 1:1 in dehydratedtetrahydrofuran, is added dropwise a stoichiometric amount of water(e.g. H₂O or D20) in THF at 0° C. (nonstoichiometric amounts, higher orlower, can also be used). After stirring for 1 hour, the solution isneutralized with 3 equivalents, of sodium hydrogencarbonate. Afterconfirming the completion of generation of carbonic acid gas from thereaction solution, the solution is filtered and volatile compounds areremoved by vacuum evaporation to obtain colorless, transparent viscousliquid, poly(pentafluorophenyltrifluorovinylsiloxane), in a threedimensional network of alternating silicon and oxygen atoms.

[0135] Example I above is but one example of a method comprising:reacting a compound of the general formula R1 MX3₃ with a compound ofthe general formula R2MX3₃ where R1 is selected from alkyl, alkenyl,aryl and alkynyl, R2 is selected from alkenyl, aryl or alkynyl, M is anelement selected from groups 3-6 or 13-16 though preferably from group14 of the periodic table, and X3 is a halogen; with H₂O or D2O; so as toform a compound having a molecular weight of from 500 to 10,000 with a-M-O-M-O— backbone with R1 and R2 substituents on each M. In thehydrolysis example above, silicon atoms of the network are modified bypentafluorophenyl and trifluorovinyl groups in an approximate ratio 1:1.Of course other ratios are possible depending upon the ratio of startingmaterials, and, of course, other three dimensional networks can beachieved by having other (or additional) starting materials selectedfrom Compound IV, VII and IX, along with other hydrolyzable materials.An alternate example is a method comprising: reacting a compound of thegeneral formula R1R2MX3₂ where R1 is selected from alkyl, alkenyl, aryland alkynyl, R2 is selected from alkenyl, aryl or alkynyl, M is anelement selected from group 14 of the periodic table, and X3 is ahalogen; with D20; so as to form a compound having a molecular weight offrom 500 to 10,000 with a -M-O-M-O— backbone with R1 and R2 substituentson each M. As mentioned above, Compounds IV, VII and IX have organic (orhybrid) R group(s) and halogen(s) (preferably Br or Cl) bound to M(selected from groups 3-6 or 13-16—preferably group 14)) and can becombined in almost limitless combinations—e.g. a compound selected fromthe Compound IV group could be hydrolyzed with another compound selectedfrom Compound IV. In another example, a single compound from CompoundVII is hydrolyzed. Many other combinations are possible, including:Compound IV+Compound VII; Compound IV+Compound IV+Compound IV; CompoundVII+Compound VII; Compound IV+Compound VII+Compound IX; CompoundIV+Compound IV+Compound IX; Compound VII+Compound IX, etc.—which variouscombinations of compounds will result in a hydrolyzed material having atleast one organic substituent bound to an inorganic oxidebackbone—preferably from 2 to 6 different organic substituents bound tothe backbone prior to deposition and exposure. The presence of theorganic groups, preferably all fluorinated, allows for improved opticalabsorption characteristics due to minimal or absent C—H bonds in thedeposited material (preferably the hydrolyzed/condensed material has ahydrogen content of 10% or less, preferably 5% or less, and morepreferably 1% or less).

[0136] Also, though “M” in the above hydrolysis example is silicon, itis possible to have materials with other M groups, or “dope” one or moresilanes to be hydrolyzed with a lesser (though not necessarily lesser)amount of a compound having a different M group such as boron, ametalloid and/or an early transition metal (e.g. B, Al, Si, Ge, Sn, Sb,Pb, Ta, Ti, Zr, Er, Yb and/or Nb). As an example, a material could beformed from hydrolyzing/condensing one or more compounds each formed ofsilicon, chlorine and one or more fluorinated organic compounds bound tothe silicon, whereas another material could be formed byhydrolyzing/condensing such compound with one or more additionalcompounds that each comprise an element other than silicon (Ge, Nb, Ybetc.), chlorine and one or more fluorinated organic groups. In this way,the inorganic backbone of the hydrolyzed/condensed material willcomprise silicon, oxygen and the element(s) other than silicon, withfluorinated organic groups bound to this backbone. This “modifiedbackbone” can result in a material refractive index different than onehaving an inorganic backbone comprising silicon and oxygen alone. Suchan ability to modify the refractive index is desirable for forming coreand cladding layers in a waveguide.

[0137] Deposition of the Hydrolyzed and Condensed Material:

[0138] The material formed as above preferably has a molecular weightbetween 500 and 10,000, more preferably between 500 and 5000. Othermolecular weights are possible within the scope of the invention,however a weight between 500 and 5000 provides the best properties fordepositing the material on a substrate. The substrate can be anysuitable substrate, such as any article of manufacture that couldbenefit from the combined benefits of a hybrid organic-inorganicmaterial. In the fields of electronics and optical communications, thematerial could be deposited as a final passivation layer, as a glob topcoating, as an underfill in a flip chip process, as a hermetic packaginglayer, etc. Because the material can be patterned as will be discussedfurther below, the material could be deposited on a substrate (e.g. aglass, quartz, silicon or other wafer) as a buffer/cladding,waveguide/core or other layer within a waveguide or otheroptoelectronic/photonic device. In general, the siloxane oligomer—thehybrid organic-inorganic material having the molecular weight as setforth above—is nixed with a suitable solvent and deposited. The solventcan be any suitable solvent, such as isopropanol, ethanol, methanol,THF, mesitylene, toluene, cyclohexanone, cyclopentanone, dioxane, methylisobutyl ketone, or perfluorinated toluene.

[0139] Deposition is generally at a temperature of 200 C or less (can beat 150 C or less). If the material is annealed after deposition, it ispreferably at 200 C or less. If the material is to be patterned byexposure to electromagnetic radiation (e.g. UV light) then aphotoinitiator can be mixed into the material along with the solvent.There are many suitable types of photoinitiators that could be used,such as Irgacure 184, Irgacure 500, Irgacure 784, Irgacure 819, Irgacure1300, Irgacure 1800, Darocure 1173 or Darocure 4265. The initiator couldbe highly fluorinated, such as 1,4-bis(pentafluorobenzoyl)benzene orRhodosil 2074 photoinitiator. Also, thermal initiators can be appliedfor thermal crosslinking of organic carbon double bond moieties, such aswith Benzoyl peroxide, 2,2′-Azobisisobutyronitrile, or tert-Butylhydroperoxide. The amount of these photo or thermal initiators may varyfrom 0. 1 to 5 w-%. They may appear in solid or liquid phase. Theinitiator is carefully mixed with the material that already contains“processing solvent”. (Organic dopants or liquid crystal dopants—orerbium—can be mixed with the material at this point if desired.) Finallythe material is filtered through inert semiconductor grade filter toremove all undissolved material.

[0140] Spin-on processing. After hydrolysis and condensation, thematerial solution is deposited on a substrate in a spin-on process (orby dipping, spray and meniscus coating, etc.). Both static and dynamicdeposition can be used. The material is first spread over a wafer orother substrate at low speed (50 to 700 rpm) for 5 to 10 seconds andthen the speed is increased by 500 to 5000 rpm/s acceleration to 1000rpm or higher depending upon starling speed. However, slower speeds maybe used if very thick films are required. If 1000 rpm spinning speed isapplied film thicknesses from 100 nm to 30,000 nm are achieved dependingon material viscosity. Material viscosity can be tuned by increasing theamount of process solvent, which typically have relative low vaporpressure and high boiling point. Spinning is continued for 30 to 60seconds to obtain uniform film over the wafer. After the spinning, anedge bead removal process is accomplished and the wafer is pre-baked (innitrogen on hot-plate or in furnace) at temperature around 100 Celsiusfor 1 minute to remove the process solvent (if used) and improveadhesion to the substrate or to the layer underneath of the currentmaterial. Similar spin cycles are applicable for all three main opticallayers, which are buffer, core and cladding layers. Adhesion promotersuch as 1% aminopropyltrimethoxy silane in IPA or plasma activation maybe applied between the main optical layers to improve adhesion betweenthen.

[0141] The substrate can be any suitable substrate or article. In manycases, the substrate will be a planar wafer-type substrate, such as aglass, plastic, quartz, sapphire, ceramic or a semiconductor substrate(e.g. germanium or silicon). The substrate can have electronic orphotonic circuitry thereon. For example, the substrate could be anintegrated circuit or a printed circuit board. Or, a light emittor orphotodetector could be provided on the substrate prior to deposition ofthe hybrid material of the invention (or such an additional opticalcomponent could be “dropped in” after deposition of the material. Thephotodetector could be an avalanche photodiode or PIN diode, whereas thelight emittor could be a laser (e.g. VCSEL) or LED (e.g. OLED). Or, thelight emittor could be a monolithic Fabry-Perot laser, a monolithicBragg laser, a monolithic distributed feedback laser or a semconductorquantum well laser. The light emittor could also be a single frequencylaser (e.g. a distributed feedback laser) or a multi-frequency laser(e.g. an integrated cavity laser or an arrayed laser).

[0142] There is essentially no limit to the number or types of photonicor electronic devices that could be integrated with the depositedmaterial—whether the material is used as a simple coating or passivationlayer, or as a waveguide (of course, if the material forms the claddingand/or core layers of a waveguide, it is preferable that the otheroptical component(s) is disposed so as to properly direct or receivelight into or out of the waveguide (in a simple example, the waveguideacts as a coupler between a fiber and the photodetector or lightemittor). Other optical devices that could be formed on the substrate,or in communication with the waveguide, include N-port splitters withcascading Y couplers, planar crossovers, amplifiers, switches,wavelength division multiplexor receiver assemblies, arrayed waveguidegratings, PIN diode receivers, external modulators, combiners,amplifiers (e.g. multistage EDFA), isolators, resonant couplers,wavelength couplers or splitters, waveguide grating routers, filters,integrated EDWAs, monolithic DCMs, reonfigurable OADMs, optical channelmonitors, thermo optic VOAs, dispersion compensators, gain flatterners,tunable waveguide gratings, waveguide polarizers, splitters,interleavers, taps, etc. Or, the material of the invention could be usedto form the optical device components themselves, if desired.

[0143] Deposition Example 1: Add 10 w-% of methyl isobutyl ketone and 1w-% of Darocure 1173 photoinitiator to result in the formation of aspin-coatable and photo-sensitive material. The material is deposited byspin coating, spray coating, dip coating, etc. onto a substrate or otherarticle of manufacture. As mentioned herein, many other organic groupscan be used in place of the above groups, though preferably one of thegroups in one of the compounds is capable of cross linking when exposedto electromagnetic energy (or an electron beam)—e.g. an organic groupwith a ring structure (e.g. an epoxy) or a double bond (e.g. vinyl,allyl, acrylate, etc.). And, preferably such a cross linking group ispartially or fully fluorinated so that the organic cross linking groupsin the material after cross linking will be fluorinated cross linkinggroups—ideally perfluorocarbon cross linking groups in the finallyformed material.

[0144] Exposure:

[0145] One use of the material set forth above is as a layer within awaveguide. However, as mentioned elsewhere herein, many other devices,from simple hybrid coatings to complex optical devices, can be formedfrom the materials and methods described above. In the most simple form,as can be seen in FIG. 1, the material of the invention is deposited ona substrate (any suitable substrate, including light transmissivesubstrates, silicon wafers, or any other suitable article), followed byexposure to e.g. UV light (or e beam) and removal of non-exposed areas.Regardless of the article being formed, it will be desirable to crosslink the deposited material. As mentioned above, any suitable crosslinking agent can be used, including common thermal and photoinitiators. Assuming that a photoinitiator has been used, then thedeposited core layer material acts as a negative tone photoresist, i.e.exposed regions becomes less soluble in a developer. The depositedmaterial can be exposed with any suitable electromagnetic energy, thoughpreferably having a wavelength from 13 nm to 700 nm, including DUV(210-280 nm), mid-UV (280-310 nm), standard I-line or G-line UV-light.DUV exposure is preferred. A stepper can be used for the UV exposure.Typically contact mask exposure techniques are applied. Exposure timesmay vary between 1 second to several hundred seconds. After the exposurethe unexposed areas are removed by soaking the substrate/article (e.g.wafer) or otherwise exposing the substrate/article to a suitabledeveloper (e.g. spray-development may also be used). A developer such asDow Chemical DS2100, Isopropanol, methyl isobutyl ketone etc. or theircombinations can be used to remove unexposed material. Typically 2minutes development time is used and a solvent rinse (e.g. an ethanolrinse) is preferred to finalize the development. The rinsing removesdevelopment residues from the wafer. The adhesion of the exposedstructures and the effectiveness of the exposure can be increased byheat-treating the article/substrate (e.g. a slow anneal at elevatedtemperature—typically less than 200 C). Other exposure techniques, suchas exposure with a laser or with Deep UV, could also be performed inplace of the above.

[0146] Post-baking process. The final hardening of the material isachieved by baking (in air, nitrogen, argon or helium) thearticle/substrate for several hours typically at less than 200 C.Step-wise heating ramp-up and ramp-down are preferred. The material canalso be fully or partially hardened with deep UV light curing.

[0147] In the alternative to the above, the material to be patterned isspun on, prebaked, hard baked (typically less than 200 C). Then standardphotoresist and RIE etching techniques are applied.

[0148] Waveguide:

[0149] If the article being formed is a waveguide, the substrate couldbe a PCB, IC, silicon, glass or quartz wafer, etc., upon which isdeposited a lower cladding layer. (A buffer layer can first be depositedif desired.) The cladding layer is made by forming Compounds IV, VIIand/or IX and hydrolyzing such compound(s), followed by mixing thehydrolyzed material with a solvent and thermal initiator and thendepositing onto the substrate, as set forth in further detail above.After deposition, the cladding layer can be exposed to UV light and/orbaked to solidify the cladding. On the cladding layer is deposited acore layer that is made and deposited as above, except with a differentratio of compounds or different compounds that are hydrolyzed/condensedto form the material ready for deposition. By modifying the hydrolysablecompounds and/or ratios of compounds in the core layer vs. those in thecladding layer, a different index of refraction is achieved. A developer(e.g. e.g. methanol, ethanol, propanol, acetone, methyl isobutyl ketone,tetrahydrofuran, Dow Chemical DS2100, Dow Chemical DS3000, etc.) is thenapplied to remove unexposed material. In this way, a core for thewaveguide is formed. Then an upper cladding layer is made and depositedin the same way as the lower cladding layer. Though in this example themask is a binary mask (the material is either fully exposed or notexposed to electromagnetic radiation), it is also possible to providepartial exposure (e.g. in a continuum from full exposure to a low ornon-exposure level as in a gray scale mask). Such a gray scale exposurecan form a vertical taper in the waveguide when the developer isapplied.

[0150] More particularly, as can be seen in FIG. 2A, a substrate 10 isprovided, on which is deposited a lower cladding layer 12 (FIG. 2B). Abuffer layer could be deposited prior to depositing the lower claddinglayer, depending in part on the thickness of the lower cladding layerthat is deposited. After depositing the lower cladding layer, a corelayer 14 is deposited (FIG. 2C). Core layer 14 preferably has adifferent refractive index than the lower cladding layer. Core layer 14is then patterned, preferably by exposure to light (preferably UV light)via a mask 20 (FIG. 2D). Areas that are exposed to light undergo crosslinking and hardening. As can be seen in FIG. 2E, application of adeveloper allows for removal of unexposed areas, with exposed areas 141of the core layer remaining (now the core). Baking/annealing can be usedto stabilize the remaining areas of the core layer. As can be seen inFIG. 2F, an upper cladding layer 16 is deposited, followed by a finalhard bake. Preferably upper cladding layer 16 has a different refractiveindex than core 141, which refractive index can be the same as that ofthe lower cladding layer 12. A cross section photograph of a patternedcore, in accordance with the method of FIGS. 2A to 2F, is illustrated inFIG. 4.

[0151] An alternate process for forming a waveguide is illustrated inFIG. 3A, a substrate 30 is provided, upon which is deposited a lowercladding layer 32 (FIG. 3B). As above, a buffer layer could also beprovided, prior to depositing the lower cladding layer, if desired. Thesubstrate and any layers thereon can be heated to stabilize thedeposited layer(s). As can be seen in FIG. 3C, a core layer 34 isprovided preferably having a refractive index different than therefractive index of the lower cladding layer. Then, as can be seen inFIG. 3D, a photoresist layer 36 (e.g. positive tone) is deposited(preferably by spin-on), followed by a pre-bake. Then, the photoresistis exposed to electromagnetic radiation in FIG. 3E (e.g. UVlight—wavelength depending upon the type of photoresist selected), andexposed to a developer (FIG. 3F) to remove exposed areas of resist,leaving behind unexposed resist areas 36 ¹. Then, core layer 34 isetched, such as by reactive ion etching, so as to remove areas of corelayer not protected by resist areas 36 ¹—leaving behind core layerportion 34 ¹. Finally, resist portions 36 ¹ are removed, and, asillustrated in FIG. 3H, an upper cladding layer 38 is deposited,followed by heating of the thus formed waveguide. Any of the claddinglayers and core layer (as well as buffer layer if included) can beformed of the hybrid material of the invention. Of course, the claddinglayers preferably have a different refractive index than the core, whichrefractive index can be achieved by modifying the inorganic backboneand/or the organic groups bound thereto, as mentioned elsewhere herein.Material Characteristics:

[0152] Material processed and formed on a substrate as above, was testedto determine various characteristics of the deposited and cross linkedmaterial. As will be seen below, some tests were performed on thematerial in “bulk form”—e.g. by testing deposited material on asubstrate. Other tests were performed after patterning and forming awaveguide. For example, the stability of the material was determinedbased on bulk measurement tests. Stability of deposited materials of theinvention was determined by the so-called “pressure cooking” testingprocedure. In this procedure, the material was deposited on a substrateand, after cross linking (thermal and/or light exposed cross linkingdepending upon the initiator used), tested for optical properties suchas optical absorbance, polarization dependent loss and refractive index.Then, the material was placed into a pressure chamber that contains anamount of water. The chamber was heated up to 120 C and maintained at apressure of 2 atm, at which point the water formed supercritical watervapor. The material was held in this environment for 2 hours and thenremoved and tested optically (optical absorbance, polarization dependentloss and refractive index). It was found that the material was stillpresent on the substrate and had not been changed structurally. Also,the optical testing showed that optical absorbance, polarizationdependent loss and index of refraction each remained within 5% (in mostcases within 2%) of the original values prior to the exposure to thesupercritical water. The testing showed a high level of stability notnormally found in optical materials having an organic component such asthe materials of the present invention.

[0153] In testing contact angle, a bulk measurement was made afterforming a layer on a substrate. In a test of the hydrophobicity of thehybrid material, a water contact angle measurement can be measured. Thephenomenon of wetting or non-wetting of a solid by a liquid can beunderstood in terms of the contact angle. A drop of a liquid resting ona solid surface forming an angle relative to the surface may beconsidered as resting in equilibrium by balancing the three forcesinvolved (namely, the interfacial tensions between solid and liquid,that between solid and vapor and that between liquid and vapor). Theangle within the liquid phase is known the contact angle or wettingangle. It is the angle included between the tangent plane to the surfaceof the liquid and the tangent plane to the surface of the solid, at anypoint along their line of contact. The surface tension of the solid willfavor spreading of the liquid, but this is opposed by the solid-liquidinterfacial tension and the vector of the surface tension of the liquidin the plane of the solid surface.

[0154] In the present invention, contact angles of 90 degrees or more,and generally 100 degrees or more are easily achieved (from 50 ul ofultrapure water). Depending upon the compounds selected forhydrolysis/condensation, water contact angles of 125 degrees or more, oreven 150 degrees or more can be achieved. Particularly if all organicgroups, including those that provide bulk to the final material (e.g. alonger alkyl chain or a single or multi ring aryl group) as well asthose that allow for cross linking (e.g. organic groups with unsaturateddouble bonds), are fully fluorinated—then the resulting material can behighly hydrophobic and result in very large contact angles. Thehydrophobicity can easily be tailored depending upon which compounds areselected, and in what amounts, for hydrolysis/condensation.

[0155] The optical loss of the materials were also tested and determinedto be less than 0.1 dB/cm at 1550 mm The optical loss can be less than0.09 dB/cm (or even less than 0.075 dB/cm or less than 0.05 dB/cm) at1550 nm, depending upon which compounds and in what amounts are selectedfor hydrolysis/condensation, and in particular the level of fluorinationof the compounds selected. The deposited materials tested also have anoptical loss less than 0.1 dB/cm (or even less than 0.075 dB/cm) at 1310nm, C Band and L Band. The optical bulk loss measurement was carried outfrom bulk sample of the optical material by using Varian Gary 5UV-Vis-IR spectrophotometer.

[0156] Polarization Dependent Loss (PDL) measurements were made on aformed waveguide. Equipment used for PDL measurements, included a redlight source, a laser source, a coupler, a polarization controller,input and output single mode fibres, a detector, alignment stages, afibre coupler, a lens and a screen: Align input fibre directly to outputfibre, moving fibre holders nearer each other as required. Ensure thered light source is switched off and the polarization controller is notscanning. Dispense a bead of index matching fluid between fibres andoptimize the alignment using the laser and power meter. Ensure theaveraging time of the detector is 20 ms and the wavelength is 1550nm.Set the polarization controller scanning on scan speed 5. Wait for 10 sand record the maximum and minimum power levels. Stop the polarizationcontroller scanning. Plot the average and the PDL on the chart. Makesure values are within acceptable limits. Then, turn red light source onand laser off. Wipe the facets of the chip gently with IPA and place iton the holder. Looking through the microscope, roughly align the inputfibre to the desired waveguide. Place the lens on the output stage,about 7 mm from the output facet. Align the input fibre vertically untila red line is observed on the screen. Focus the line on the screen bymoving the lens nearer or further from the chip. Scan the input fibreacross the input of the chip until a spot is observed on the screen.Check using the microscope that the fibre is aligned to the correctwaveguide still. Then, remove the lens and replace with the outputfibre. Using the microscope, position the fibre near the desiredwaveguide, about 100 um (the width of the fibre) back from the chip.Turn the red light off and the laser on. Move the output fibrevertically until the power is maximized. Move the output fibrehorizontally until the power is maximized. Dispense a bead of indexfluid on the input and output facets. Finely adjust all axes until thepower is optimized. Then, scan the polarization controller and wait for10 seconds. Record the maximum and minimum power levels, calculating theaverage loss and the PDL. To measure the next waveguide, retract theinput and output fibres slightly and index the center stage to the nextwaveguide. The power meter will indicate when the next waveguide is inposition. Return to the ‘chip alignment’ stage. Polarization dependentloss was found to be 0.1 dB/cm or less, and generally 0.05 dB/cm orless. In some cases, the PDL was 0.01 dB/cm or less. Birefringencemeasurements were also performed on the materials.

[0157] Birefringence was found to be less than 5×e-5, and in many casesless than 2×10e−5 (or as low as 1×10e−6) depending upon the compoundsselected for hydrolysis/condensation. The birefringence of the slaboptical films were measured on a SCI FilmTech 4000.

[0158] Other properties of the materials, such as surface and sidewallroughness, feature size, aspect ratio, and glass transition temperaturewere also measured. The glass transition temperature, Tg, of thedeposited materials was measured using a Mettler-Toledo DifferentialScanning Calorimeter (DSC) and found to be 200 C or greater, andgenerally 250 C or greater (or even 310 C or more). Surface roughness,Rq, of the material (measured by atomic force microscopy and WYKO—whitelight interferometry) was found to be 10 nm or less, and generally 5 nmor less. In many cases, the surface roughness is 1 nm or less. When thematerial is patterned, sidewalls are formed in the surface topographythat is created. A measurement of the sidewall roughness (measured byatomic force microscopy, SEM and WYKO—white light interferometry) wasfound to be 50 nm or less, and generally 10 nm or less. Depending uponthe compounds used for hydrolysis/condensation, as well as exposure anddevelopment technique, a sidewall roughness, Rq, or 5 nm or less, oreven 1 nm or less, can be achieved. Patterning of the material was ableto create feature sizes (e.g. ridge or trench width) as small as 100 nmor less, or even 50 nm or less, as well as aspect ratios of suchfeatures of 2:1, 3:1 or even as high as 10:1 (also measured by atomicforce microscopy, SEM and WYKO—white light interferometry).

[0159] Due to the hydrophobic nature of some of the materials within thepresent invention (e.g. those having a higher degree of fluorination),it may be desirable in some cases to first provide an adhesion promotinglayer before depositing the hybrid material. For example, a 1:100dilution of the material of the invention could be applied as anadhesion promoting layer before spinning on (or otherwise depositing)the hybrid material. The diluted SOD is very stable (photo, thermal,humidity, 85/85 tests) and easy to detect, spreads well on Silicon andis optically clear all the way to UV

[0160] Other adhesion promoting materials that could be used includeOnichem organosilane G602, (N (beta aminoethyl)-gamma aminopropyldimethyl siloxane (CA 3069-29-2)—high boiling, high R1(1.454), thermallystable low density and is compatible with acrylics, silicones, epoxies,and phenolics), or Dow AP8000, propyloxysilane (e.g. 3(2 3 epoxy propoxypropyl) trimethoxy silane), Ormocer (low viscosity), Halar, Orion/DupontTeflon primer, trifluoroacetic acid, barium acetate, fluorethers (fromCytonix), PFC FSM 660 (a fluoroalkyl monosilane in a fluorinatedsolvent)—can be diluted to 0.1 to 0.05 percent in alcohol or fluorinatedsolvent, PFC FSM 1770 (a tri-fluoroalkyl monosilane in a fluorinatedsolvent, providing very low surface energy to oxide surfaces and goodadhesion for fluoropolymers)—can be diluted to 0.1 to 0.05 percent inalcohol or fluorinated solvent, and/or HMDS.

[0161] The materials of the invention can be deposited as very thinlayers (as thin as from 1 to 10 molecular layers), or in thicker filmsfrom 1 nm up to 100 um (or more). Generally, the material is depositedat a thickness of from 0.5 to 50 un, preferably from 1 to 20 um—thoughof course the thickness depends upon the actual use of the material(waveguide, passivation coating, adhesive, etc.). The thickness of thedeposited layer can be controlled by controlling the material viscosity,solvent content and spinning speed (if deposited by spin on). Materialthickness can also be controlled by adjusting the deposition temperatureof both the deposition solution and the spinner (if spin on deposition).Also, adjusting the solvent vapor pressure and boiling point byselection of solvent can affect the thickness of the deposited material.Spin on deposition can be performed on a Karl Suss Cyrset enhanced RC8spinner. Spray coating, dip-coating, meniscus coating, screen printingand “doctor blade” methods can also be used to achieve films of varyingthickness.

[0162] This invention has been described in connection with thepreferred embodiments. Many variations of the above embodiments arecontemplated as being within the scope of the invention.

We claim:
 1. A method for making a waveguide, comprising: providing asubstrate; forming a lower cladding layer on the substrate; forming acore layer above the lower cladding layer; and forming an upper claddinglayer above the core layer; wherein the lower cladding layer, core layerand/or upper cladding layer is a stable layer that comprises a materialthat is capable of being heated in supercritical water vapor at 2 atmand at 120 C for 2 hours after which optical absorption, polarizationdependent loss and/or refractive index change remains unchanged ±5%. 2.The method of claim 1, wherein the stable layer is hydrophobic andresults, if exposed to water, in a water contact angle of 90 degrees ormore.
 3. The method of claim 1, wherein the material of the stable layeris formed by depositing at a temperature of 200 C or less.
 4. The methodof claim 3, wherein the material of the stable layer is annealed afterdepositing, wherein the annealing is at a temperature of 200 C or less.5. The method of claim 3, wherein the material of the stable layer isdeposited at a temperature of 150 C or less.
 6. The method of claim 1,wherein the substrate is an integrated circuit substrate.
 7. The methodof claim 1, wherein the substrate is a glass, quartz, semiconductor,ceramic or plastic substrate.
 8. The method of claim 7, wherein thesubstrate is a glass or quartz substrate.
 9. The method of claim 7,wherein the substrate is a semiconductor substrate.
 10. The method ofclaim 9, wherein the substrate is a silicon or germanium substrate. 11.The method of claim 7, wherein the substrate comprises photonic and/orelectronic circuitry thereon.
 12. The method of claim 11, wherein thecircuitry is formed on the substrate prior to depositing the lowercladding layer.
 13. The method of claim 1, wherein the substrate is aprinted circuit board.
 14. The method of claim 1, wherein the stablelayer has an optical loss of less than 0.1 dB/cm at 1550 nm.
 15. Themethod of claim 14, wherein the stable layer has an optical loss of lessthan 0.09 dB/cm at 1550 nm.
 16. The method of claim 15, wherein thestable layer has an optical loss of less than 0.075 dB/cm at 1550 nm.17. The method of claim 1, wherein the stable layer has an optical lossof less than 0.1 dB/cm at 1310 nm.
 18. The method of claim 1, whereinthe stable layer has an optical loss of less than 0.1 dB/cm at C Band.19. The method of claim 1, wherein the stable layer has an optical lossof less than 0.1 dB/cm at L Band.
 20. The method of claim 16, whereinthe stable layer has an optical loss of less than 0.05 dB/cm at 1550 nm.21. The method of claim 1, wherein the lower cladding layer, core layerand/or upper cladding layer is a stable layer that comprises a materialthat is capable of being heated in supercritical water vapor at 2 atmand at 120 C for 2 hours after which optical absorption remainsunchanged ±5%.
 22. The method of claim 1, wherein the lower claddinglayer, core layer and/or upper cladding layer is a stable layer thatcomprises a material that is capable of being heated in supercriticalwater vapor at 2 atm and at 120 C for 2 hours after which polarizationdependent loss remains unchanged ±5%.
 23. The method of claim 1, whereinthe lower cladding layer, core layer and/or upper cladding layer is astable layer that comprises a material that is capable of being heatedin supercritical water vapor at 2 atm and at 120 C for 2 hours afterwhich the refractive index remains unchanged ±5%.
 24. The method ofclaim 1, wherein the material that is capable of being heated illsupercritical water vapor at 2 atm and at 120 C for 2 hours is a hybridorganic inorganic material.
 25. The method of claim 1, wherein thestable material has a birefringence of less than 5×10e−5.
 26. The methodof claim 25, wherein the stable material has a birefringence of lessthan 2×10e−5.
 27. The method of claim 26, wherein the stable materialhas a birefringence of less than 1×10e−6.
 28. The method of claim 1,wherein the stable material is directly patterned to have a surfacetopography where the aspect ratio is at least 2:1.
 29. The method ofclaim 28, wherein the stable material is directly patterned to have asurface topography where the aspect ratio is at least 3:1.
 30. Themethod of claim 29, wherein the deposited stable material is directlypatterned to have a surface topography where the aspect ratio is atleast 10:1.
 31. The method of claim 1, wherein the deposited stablematerial is deposited at a rate of 100 um/min or more.
 32. The method ofclaim 1, wherein the deposited stable material has a thickness of from 1nm to 100 nm after a single deposition step.
 33. The method of claim 32,wherein the deposited stable material has a thickness of from 0.5 um to50 um after a single deposition step.
 34. The method of claim 1, whereinthe deposited stable material has a thickness of from 1 um to 20 umafter a single deposition step.
 35. The method of claim 1, wherein thestable material has a polarization dependent loss of 0.1 dB/cm or less.36. The method of claim 35, wherein the deposited stable material has apolarization dependent loss of 0.05 dB/cm or less.
 37. The method ofclaim 36, wherein the stable material has a polarization dependent lossof 0.01 dB/cm or less.
 38. The method of claim 1, wherein the stablematerial has a glass transition temperature or 200 C or greater.
 39. Themethod of claim 1, wherein the stable material is perfluorinated. 40.The method of claim 1, wherein the stable material is comprised of lessthan 10% H.
 41. The method of claim 40, wherein the stable material iscomprised of less than 5% H.
 42. The method of claim 41, wherein thestable material is comprised of less than 1% H.
 43. The method of claim1, wherein the stable material is both the core layer and at least oneof the lower and upper cladding layers, wherein the refractive index ofthe core layer and the at least one lower and upper cladding layers isfrom 0.1% to 3%.
 44. The method of claim 43, wherein the at least onelower and upper cladding layers and the core layer are both hybridorganic inorganic layers but differing from each other in the organicand/or inorganic components.
 45. The method of claim 1, wherein thedifference in refractive index between the core and cladding layers isgreater than 1%.
 46. The method of claim 1, wherein the stable materialhas a surface roughness Rq of 10 nm or less.
 47. The method of claim 46,wherein the stable material has a surface roughness Rq of 5 um or less.48. The method of claim 47, wherein the stable material has a surfaceroughness Rq of 1 nm or less.
 49. The method of claim 1, wherein thedeposited stable material is patterned and has a sidewall roughness Rqof 50 nm or less.
 50. The method of claim 49, wherein the stablematerial is patterned and has a sidewall roughness Rq of 10 nun or less.51. The method of claim 50, wherein the stable material is patterned andhas a sidewall roughness Rq of 5 nm or less.
 52. The method of claim 51,wherein the stable material is patterned and has a sidewall roughness Rqof 1 nm or less.
 53. The method of claim 1, wherein the stable materialis patterned to form apertures and/or ridges having a feature size of100 nm or less.
 54. The method of claim 53, wherein the stable materialis patterned to form apertures and/or ridges having a feature size of 50nm or less.
 55. The method of claim 1, wherein at least a portion of thestable material is a fluorinated organic moiety.
 56. The method of claim1, wherein at least a portion of the stable material is an inorganicmoiety.
 57. The method of claim 56, wherein the inorganic moiety is ametal oxide backbone.
 58. The method of claim 1, wherein the stablematerial is deposited by spin coating, spray coating or dip coating. 59.The method of claim 58, wherein the stable material is deposited by spincoating.
 60. The method of claim 58, wherein the stable material isdeposited by spray coating.
 61. The method of claim 2, wherein thedeposited stable material has a hydrophobicity that results in a watercontact angle of 100 degrees or more.
 62. The method of claim 61,wherein the deposited stable material has a water contact angle of 125degrees or more.
 63. The method of claim 62, wherein the depositedstable material has a water contact angle of 150 degrees or more. 64.The method of claim 1, wherein the stable material is directly patternedby application of electromagnetic energy and a developer, prior todepositing the upper cladding layer.
 65. The method of claim 1, whereinthe stable material comprises an organic dopant or an inorganic liquidcrystal dopant.
 66. The method of claim 1, wherein the refractive indexof the stable material is tunable by application of UV light, visiblelight, infrared light, X-rays, electron beam or ion beam prior todepositing the upper cladding layer.
 67. The method of claim 1, whereinthe deposited stable material has a glass transition temperature of 200C or more.
 68. The method of claim 67, wherein the deposited stablematerial has a glass transition temperature of 250 C or more.
 69. Themethod of claim 68, wherein the deposited stable material has a glasstransition temperature of 310 C or more.
 70. The method of claim 1,wherein the deposited stable layer has a thermo-optic coefficient(dn/dT) greater than |10×10e5 |.
 71. The method of claim 1, wherein thestable layer is directly patterned by exposure to electromagnetic energyvia a gray scale mask, followed by removal of a portion of the stablelayer with a developer.
 72. The method of claim 1, wherein the stablelayer is patterned, the patterning of the stable layer comprisesdirecting electromagnetic energy at the stable layer followed byproviding a developer to remove portions of the stable layer.
 73. Themethod of claim 1, wherein the stable material is formed with arepeating -M-O-M-O— backbone having at least one organic substituent,the material having a molecular weight of from 500 to 10000, where M isboron, a metalloid or a metal, and O is oxygen.
 74. The method of claim73, wherein the molecular weight is from 1500 to
 3000. 75. The method ofclaim 74, wherein the organic substitutent is fully fluorinated.
 76. Themethod of claim 75, wherein more than one different organic substituentis bound to the repeating -M-O-M-O backbone, and wherein each organicsubstituent is fully or partially fluorinated.
 77. The method of claim76, wherein the stable material comprises organic cross linking groupsbetween adjacent -M-O-M-O— strands.
 78. The method of claim 73, whereinthe organic cross linking groups are fully or partially fluorinated. 79.The method of claim 78, wherein the organic cross linking groups arepeifluorinated groups.
 80. The method of claim 73, wherein the at leastone organic substitutent is a single or multi ring aryl group or analkyl group having 5 or more carbons.
 81. The method of claim 80,wherein the aryl or alkyl group is fluorinated or deuterated.
 82. Themethod of claim 81, wherein the aryl or alkyl group is fluorinated. 83.The method of claim 82, wherein the at least one organic substituent isa fluorinated phenyl or fluorinated C₁-C₅ alkyl group.
 84. The method ofclaim 83, wherein the fluorinated phenyl group is substituted withfluorinated methyl, ethyl or alkenyl groups.
 85. The method of claim 73,wherein M is B, Al, Si, Ge, Sn, Sb, Pb, Ta, Ti, Zr, Er, Yb and/or Nb.86. The method of claim 85, wherein M is B, Al, Si, Ge, Sn, Sb or Pb.87. The method of claim 86, wherein M is Ta, Ti, Zr or Nb.
 88. Themethod of claim 87, wherein M is B, Al and/or Si.
 89. The method ofclaim 73, wherein the at least one organic substituent is a straight orbranched chain having 5 or more carbons.
 90. The method of claim 73,wherein either the at least one organic substituent is an aryl groupthat is a single ring or polycyclic aromatic substituent.
 91. The methodof claim 90, wherein the at least one organic substituent is a fully orpartially fluorinated single ring or polycyclic aromatic substituent.92. The method of claim 91, wherein either the at least one organicsubstituent has one or two rings.
 93. The method of claim 1, wherein thestable layer is deposited by spinning or spraying onto the substrate,the stable layer comprising a material having a molecular weight of from500 to
 10000. 94. The method of claim 93, further comprising baking thestable material after depositing onto the substrate.
 95. The method ofclaim 94, wherein the material is exposed to the electromagneticradiation via the gray scale mask so as to selectively further crosslink the material and increase the molecular weight of the material inselected areas.
 96. The method of claim 95, wherein the electromagneticenergy has a wavelength of from 13 nm to 700 nm.
 97. The method of claim95, wherein a developer is applied to remove material in unexposedareas.
 98. The method of claim 93, wherein the material is depositedafter mixing with a solvent.
 99. The method of claim 98, wherein thesolvent is selected from isopropanol, ethanol, methanol, THF,mesitylene, toluene, cyclohexanone, cyclopentanone, dioxane, methylisobutyl ketone, or perfluorinated toluene.
 100. The method of claim 88,wherein M is Si.
 101. The method of claim 98, wherein the material ismixed with a solvent and a thermal initiator or photoinitiator prior todeposition.
 102. The method of claim 101, wherein a photoinitiator ismixed with the material and solvent prior to spin on, the photoinitiatorundergoing free radical formation when exposed to light so as to causepolymerization in the stable material.
 103. The method of claim 96,wherein the electromagnetic energy is ultraviolet light.
 104. The methodof claim 103, wherein the ultraviolet light is directed on the stablelayer via a mask so as to expose portions of the stable layer, andwherein the developer removes non-exposed portions of the stable layer.105. The method of claim 1, wherein the lower cladding layer and/orupper cladding layer comprises a hybrid organic-inorganic material. 106.The method of claim 1, further comprising providing a light emittor orphotodetector on the substrate proximate to the waveguide.
 107. Themethod of claim 106, wherein the photodetector is an avalanchephotodiode or a PIN diode
 108. The method of claim 106, wherein thelight emittor is a laser or LED.
 109. The method of claim 106, whereinthe laser is a VCSEL.
 110. The method of claim 106, wherein the lightemittor is a monolithic Fabry-Perot laser, a monolithic Bragg laser, amonolithic distributed feedback laser or a semiconductor quantum welllaser.
 111. The method of claim 106, wherein the light emittor is asingle-frequency laser.
 112. The method of claim 111, wherein the singlefrequency laser is a distributed feedback laser.
 113. The method ofclaim 108, wherein the light emittor is a multi-frequency laser. 114.The method of claim 112, wherein the multi-frequency laser is anintegrated cavity laser or an arrayed laser
 115. The method of claim 1,wherein the substrate is a semiconductor, glass or plastic substrate.116. The method of claim 115, wherein the substrate is a siliconsubstrate.
 117. The method of claim 1, wherein the waveguide is formedas a coupler between a fiber and a photodetector or light emittor. 118.The method of claim 73, wherein the stable material comprisesfluorinated cross linking groups between M elements in a threedimensional -M-O-M-O— lattice.
 119. The method of claim 118, wherein theorganic cross linking group is fully fluorinated.
 120. The method ofclaim 73, comprising three or more different organic groups bound to the-M-O-M-O— backbone.
 121. The method of claim 73, further comprising adopant D that is a metalloid or early transition metal and is differentfrom M, and is bound to the -M-O-M-O— lattice and alters the refractiveindex of the stable material compared to an -M-O-M-O— lattice without adopant.
 122. The method of claim 121, wherein the dopant is an earlytransition metal.
 123. The method of claim 122, wherein the dopant istantalum, zirconium, germanium or titamium.
 124. The method of claim121, wherein the dopant is a metalloid.
 125. The method of claim 124,wherein the dopant is germanium.
 126. The method of claim 1, wherein thedeposited stable material is capable of being heated in supercriticalwater vapor at 2 atm and at 120 C for 2 hours after which opticalabsorption, polarization dependent loss and refractive index changeremain unchanged ±2%.
 127. The method of claim 1, wherein the depositedstable material is capable of being heated in supercritical water vaporat 2 atm and at 120 C for 2 hours after which the chemical stricture ofthe stable material is less than 5% changed.
 128. The method of claim 1,wherein the deposited stable material is capable of being heated insupercritical water vapor at 2 atm and at 120 C for 2 hours after whichthe chemical structure of the stable material is less than 2% changed.129. The method of claim 1, wherein the waveguide is part of an N-portsplitter with cascading Y-couplers.
 130. The method of claim 1, whereinthe waveguide is part of a planar crossover.
 131. The method of claim 1,wherein the waveguide is formed as part of an integrated opticalcircuit.
 132. The method of claim 131, wherein the integrated opticalcircuit comprises one or more of a light emittor, a photodetector, anamplifier and a switch.
 133. The method of claim 1, wherein thewaveguide is formed within a multi-device assembly on a singlesubstrate.
 134. The method of claim 133, wherein the multi-deviceassembly is a wavelength division multiplexor receiver assembly. 135.The method of claim 134, wherein the wavelength division multiplexorreceiver assembly comprises one or more arrayed waveguide gratings, anamplifier, and one or more PIN diode receivers.
 136. The method of claim133, wherein the multi-device assembly comprises a plurality of lasers,a plurality of external modulators, a combiner and amplifier.
 137. Themethod of claim 1, further comprising fabricating a photodetector orlight emittor proximate to the waveguide on the substrate.
 138. Themethod of claim 1, further comprising dropping ill a prefabricatedphotodetector or light emittor proximate to the waveguide.
 139. Themethod of claim 1, wherein the waveguide is formed as a coupler betweena fiber and either a photodetector or light emittor.
 140. The method ofclaim 1, wherein the stable layer material is doped.
 141. The method ofclaim 140, wherein the dopant is erbium.
 142. The method of claim 1,wherein the waveguide formed is part of an EDFA.
 143. The method ofclaim 142, wherein the EDFA is a multistage EDFA.
 144. The method ofclaim 1, wherein the waveguide is part of a coupler.
 145. The method ofclaim 144, wherein the coupler is a resonant coupler.
 146. The method ofclaim 1, wherein the waveguide is part of a wavelength coupler orsplitter.
 147. The method of claim 1, wherein the waveguide is part ofan isolator.
 148. The method of claim 1, wherein the waveguide is aportion of a waveguide grating router.
 149. The method of claim 1,wherein the waveguide is part of a filter, modulator or switch.
 150. Themethod of claim 1, wherein the waveguide is within a gain compensatordev., integrated EDWA, monolithic DCM, reconfigurable OADM, or opticalchannel monitor.
 151. The method of claim 1, wherein the waveguide ispart of a concentrator chip, AWG multiplexor chip, thermo optic VOA,dispersion compensator, gain flattening filter, tunable waveguidegrating, switch, coupler, modulator, waveguide polarizer, splitter,interleaver, isolator or tap.
 152. The method of claim 1, wherein thestable material is a siloxane.
 153. The method of claim 1, wherein atleast the core layer is the stable layer.
 154. The method of claim 1,wherein at least one of the cladding layers is the stable layer. 155.The method of claim 1, further comprising a passivation layer on theupper cladding layer.
 156. The method of claim 153, wherein the lowercladding layer, the upper cladding layer and the core layer are thestable layers.
 157. The method of claim 73, wherein the stable materialcomprises between 2 and 6 different organic substituents on an inorganicthree dimensional backbone matrix.
 158. The method of claim 93, whereinthe molecular weight is from 500 to
 5000. 159. The method of claim 158,wherein the molecular weight is from 500 to
 3000. 160. The method ofclaim 1, wherein the stable layer is patterned with a laser.
 161. Themethod of claim 105, wherein the stable material is fully or partiallyfluorinated.
 162. The method of claim 108, wherein the LED is an OLED.163. The method of claim 1, wherein the stable material has an opticalloss of 0.1 dB/cm at 1550 nm, is deposited at 200 C or less, apolarization dependent loss of 0.1 dB/cm or less and a surface roughnessof 10 nm or less.
 164. The method of claim 1, further comprising forminga buffer layer on the substrate before forming the lower cladding layer.165. The method of claim 164, wherein the buffer layer has ahydrophobicity that results in a contact angle of 90 degrees or more ifexposed to water.
 166. The method of claim 1, wherein the core layer isformed by depositing a core material followed by patterning the corematerial to form an elongated core.
 167. The method of claim 166,wherein the patterning of the core material is by direct ultravioletlight patterning.
 168. The method of claim 1, wherein the waveguideformed is an optical waveguide for UV, visible and/or ultraviolet light.169. The method of claim 1, wherein the stable material has a thicknessof from 1 to 10 molecular layers.
 170. The method of claim 73, whereinthe repeating -M-O-M-O— backbone is a three dimensional matrix.
 171. Themethod of claim 170, wherein both the core layer and the cladding layershave a repeating -M-O-M-O— backbone with organic substituents, but whereone or more metals “M” in the core layer backbone are different or indifferent amounts than in the cladding layers.
 172. The method of claim170, wherein both the core layer and the cladding layers have arepeating -M-O-M-O— backbone with one or more organic substitutentsbound thereto, but where the one or more organic substutituents in thecore layer are different or in different amounts than in the claddinglayers.
 173. A waveguide made by the method of claim
 1. 174. Awaveguide, comprising: a substrate; a waveguide layer, wherein thewaveguide layer comprises a hybrid organic-inorganic material, whereinthe material is capable of being heated in supercritical water vapor at2 atm and at 120 C for 2 hours after which optical absorption,polarization dependent loss and/or refractive index change remainsunchanged ±5%.
 175. The waveguide of claim 174, further comprising alower cladding layer and an upper cladding layer proximate to saidwaveguide layer.
 176. A waveguide, comprising: a substrate; a lowercladding layer; a core layer; and an upper cladding layer; wherein thelower cladding layer, the core layer and/or the upper cladding layercomprises a material that is capable of being heated in supercriticalwater vapor at 2 atm and at 120 C for 2 hours after which opticalabsorption, polarization dependent loss and/or refractive index changeremains unchanged ±5%.
 177. The waveguide of claim 176, wherein thematerial of the stable layer is hydrophobic and results, if exposed towater, in a water contact angle of 90 degrees or more.
 178. Thewaveguide of claim 176, wherein the substrate is an integrated circuitsubstrate.
 179. The waveguide of claim 176, wherein the substrate is aglass, quartz, semiconductor, ceramic or plastic substrate.
 180. Thewaveguide of claim 179, wherein the substrate is a glass or quartzsubstrate.
 181. The waveguide of claim 179, wherein the substrate is asemiconductor substrate.
 182. The waveguide of claim 181, wherein thesubstrate is a silicon or germanium substrate.
 183. The waveguide ofclaim 176, wherein the substrate comprises photonic and/or electroniccircuitry thereon.
 184. The waveguide of claim 183, wherein thecircuitry is disposed on the substrate between the lower cladding layerand the substrate.
 185. The waveguide of claim 176, wherein thesubstrate is a printed circuit board.
 186. The waveguide of claim 176,wherein the stable layer has an optical loss of less than 0.1 dB/cm at1550 nm.
 187. The waveguide of claim 186, wherein the stable layer hasan optical loss of less than 0.09 dB/cm at 1550 nm.
 188. The waveguideof claim 187, wherein the stable layer has an optical loss of less than0.075 dB/cm at 1550 nm.
 189. The waveguide of claim 176, wherein thestable layer has an optical loss of less than 0.1 dB/cm at 1310 nm. 190.The waveguide of claim 176, wherein the stable layer has an optical lossof less than 0.1 dB/cm at C Band.
 191. The waveguide of claim 176,wherein the stable layer has an optical loss of less than 0.1 dB/cm at LBand.
 192. The waveguide of claim 188, wherein the stable layer has anoptical loss of less than 0.05 dB/cm at 1550 nm.
 192. The waveguide ofclaim 176, wherein the lower cladding layer, core layer and/or uppercladding layer is a stable layer that comprises a material that iscapable of being heated in supercritical water vapor at 2 atm and at 120C for 2 hours after which optical absorption remains unchanged ±5%. 193.The waveguide of claim 176, wherein the lower cladding layer, core layerand/or upper cladding layer is a stable layer that comprises a materialthat is capable of being heated in supercritical water vapor at 2 atmand at 120 C for 2 hours after which polarization dependent loss remainsunchanged ±5%.
 194. The waveguide of claim 176, wherein the lowercladding layer, core layer and/or upper cladding layer is a stable layerthat comprises a material that is capable of being heated insupercritical water vapor at 2 atm and at 120 C for 2 hours after whichthe refractive index remains unchanged ±5%.
 196. The waveguide of claim176, wherein the deposited stable material is capable of being heated insupercritical water vapor at 2 atm and at 120 C for 2 hours after whichoptical absorption, polarization dependent loss and/or refractive indexchange remains unchanged ±2%.
 197. The waveguide of claim 176, whereinthe stable material has a birefringence of less than 5×10e−5.
 198. Thewaveguide of claim 197, wherein the stable material has a birefringenceof less than 2×10e−5.
 199. The waveguide of claim 198, wherein thestable material has a birefringence of less than 1×10e−6.
 200. Thewaveguide of claim 176, wherein the stable material is directlypatterned to have a surface topography where the aspect ratio is atleast 2:1.
 201. The waveguide of claim 200, wherein the stable materialis directly patterned to have a surface topography where the aspectratio is at least 3:1.
 202. The waveguide of claim 201, wherein thestable material is directly patterned to have a surface topography wherethe aspect ratio is at least 10:1.
 203. The waveguide of claim 176,wherein the stable material is deposited at a rate of 100 un/min. 204.The waveguide of claim 176, wherein the stable material has a thicknessof from 0.1 um to 100 um after a single deposition step.
 205. Thewaveguide of claim 204, wherein the stable material has a thickness offrom 0.5 urn to 50 um after a single deposition step.
 206. The waveguideof claim 176, wherein the stable material has a thickness of from 1 umto 20 um after a single deposition step.
 207. The waveguide of claim176, wherein the stable material has a polarization dependent loss of0.1 dB/cm or less.
 208. The waveguide of claim 207, wherein the stablematerial has a polarization dependent loss of 0.05 dB/cm or less. 209.The waveguide of claim 208, wherein the stable material has apolarization dependent loss of 0.01 dB/cm or less.
 210. The waveguide ofclaim 176, wherein the stable material has a glass transitiontemperature or 200 C or greater.
 211. The waveguide of claim 176,wherein the stable material is perfluorinated.
 212. The waveguide ofclaim 176, wherein the stable material is comprised of less than 10%) H.213. The waveguide of claim 212, wherein the stable material iscomprised of less than 5% H.
 214. The waveguide of claim 213, whereinthe stable material is comprised of less than 1% H.
 215. The waveguideof claim 176, wherein the stable material has a tunable refractiveindex.
 216. The waveguide of claim 176, wherein the stable material isboth the core layer and at least one of the lower and upper claddinglayers, wherein the refractive index of the core layer and the at leastone lower and upper cladding layers is from 0.1% to 3%.
 217. Thewaveguide of claim 176, wherein the stable material is both the corelayer and at least one of the lower and upper cladding layers, whereinthe refractive index of the core layer and the at least one lower andupper cladding layers is from 0.1% to 3%.
 218. The waveguide of claim176, wherein the stable material has a surface roughness Rq of 10 nm orless.
 219. The waveguide of claim 218, wherein the stable material has asurface roughness Rq of 5 nm or less.
 220. The waveguide of claim 219,wherein the stable material has a surface roughness Rq of 1 nm or less.221. The waveguide of claim 176, wherein the stable material is apatterned layer with a sidewall roughness Rq of 50 um or less.
 222. Thewaveguide of claim 221, wherein the stable material is a patterned layerwith a sidewall roughness Rq of 10 nm or less.
 223. The waveguide ofclaim 222, wherein the stable material is a patterned layer with asidewall roughness Rq of 5 nm or less.
 224. The waveguide of claim 223,wherein the stable material is a patterned layer with a sidewallroughness Rq of 1 nm or less.
 225. The waveguide of claim 176, whereinthe stable material is a patterned layer with apertures and/or ridgeshaving a feature size of 100 nm or less.
 226. The waveguide of claim225, wherein the stable material is a patterned layer with aperturesand/or ridges having a feature size of 50 nm or less.
 227. The waveguideof claim 176, wherein at least a portion of the stable material is afluorinated organic moiety.
 228. The waveguide of claim 176, wherein atleast a portion of the stable material is an inorganic moiety.
 229. Thewaveguide of claim 228, wherein the inorganic moiety is a metal oxidebackbone.
 230. The waveguide of claim 177, wherein the stable materialhas a hydrophobicity that results in a water contact angle of 100degrees or more.
 231. The waveguide of claim 230, wherein the stablematerial has a water contact angle of 125 degrees or more.
 232. Thewaveguide of claim 231, wherein the stable material has a water contactangle of 150 degrees or more.
 233. The waveguide of claim 176, whereinthe stable material comprises an organic dopant or an inorganic liquidcrystal dopant.
 234. The waveguide of claim 176, wherein the stablematerial has a glass transition temperature of 200 C or more.
 235. Thewaveguide of claim 234, wherein the stable material has a glasstransition temperature of 250 C or more.
 236. The waveguide of claim235, wherein the stable material has a glass transition temperature of310 C or more.
 237. The waveguide of claim 176, wherein the stable layerhas a thermo-optic coefficient greater than |10×10e5 |.
 238. Thewaveguide of claim 176, wherein the stable material comprises arepeating -M-O-M-O— backbone having at least one organic substituent,the material having a molecular weight of from 500 to 10000, where M isboron, a metalloid or a metal, and O is oxygen.
 239. The waveguide ofclaim 238, wherein the molecular weight is from 1500 to
 3000. 240. Thewaveguide of claim 238, wherein the organic substitutent is fullyfluorinated.
 241. The waveguide of claim 238, wherein more than onedifferent organic substituent is bound to the repeating -M-O-M-Obackbone, and wherein each organic substituent is fully or partiallyfluorinated.
 242. The waveguide of claim 238, wherein the stablematerial comprises organic cross linking groups between adjacent-M-O-M-O— strands.
 243. The waveguide of claim 242, wherein the organiccross linking groups are fully or partially fluorinated.
 244. Thewaveguide of claim 243, wherein the organic cross linking groups areperfluorinated groups.
 245. The waveguide of claim 238, wherein the atleast one organic substitutent is a single or multi-ring aryl group oran alkyl group having 5 or more carbons.
 246. The waveguide of claim245, wherein the aryl or alkyl group is fluorinated or deuterated. 247.The waveguide of claim 246, wherein the aryl or alkyl group isfluorinated.
 248. The waveguide of claim 238, wherein the at least oneorganic substituent is a fluorinated phenyl or fluorinated alkyl grouphaving from 1 to 5 carbons.
 249. The waveguide of claim 248, wherein thefluorinated phenyl group is substituted with fluorinated methyl, ethylor alkenyl groups.
 250. The waveguide of claim 238, wherein M is B, Al,Si, Ge, Sn, Sb, Pb, Ta, Ti, Zr, Er, Yb and/or Nb.
 251. The waveguide ofclaim 250, wherein M is B, Al, Si, Ge, Sn, Sb or Pb.
 252. The waveguideof claim 251, wherein M is Ta, Ti, Zr or Nb.
 253. The waveguide of claim252, wherein M is B, Al and/or Si.
 254. The waveguide of claim 238,wherein the at least one organic substituent is a straight or branchedchain having 5 or more carbons.
 255. The waveguide of claim 238, whereineither the at least one organic substituent is an aryl group that is asingle ring or polycyclic aromatic substituent.
 256. The waveguide ofclaim 255, wherein the at least one organic substituent is a fully orpartially fluorinated single ring or polycyclic aromatic substituent.257. The waveguide of claim 256, wherein either the at least one organicsubstituent has one or two rings.
 258. The waveguide of claim 176,wherein the stable layer comprises a material having a molecular weightof from 500 to
 10000. 259. The waveguide of claim 238, wherein M is Si.260. The waveguide of claim 176, wherein the lower cladding layer and/orupper cladding layer comprises a hybrid organic-inorganic material. 261.The waveguide of claim 176, further comprising a light emittor orphotodetector on the substrate proximate to the waveguide.
 262. Thewaveguide of claim 261, wherein the photodetector is an avalanchephotodiode or a PIN diode.
 263. The waveguide of claim 261, wherein thelight emittor is a laser or LED.
 264. The waveguide of claim 261,wherein the laser is a VCSEL.
 265. The waveguide of claim 261, whereinthe light emittor is a monolithic Fabry-Perot laser, a monolithic Bragglaser, a monolithic distributed feedback laser or a semiconductorquantum well laser.
 266. The waveguide of claim 261, wherein the lightemittor is a single-frequency laser.
 267. The waveguide of claim 266,wherein the single frequency laser is a distributed feedback laser. 268.The waveguide of claim 261, wherein the light emittor is amulti-frequency laser.
 269. The waveguide of claim 268, wherein themulti-frequency laser is an integrated cavity laser or an arrayed laser270. The waveguide of claim 176, wherein the substrate is asemiconductor, glass or plastic substrate.
 271. The waveguide of claim176, wherein the substrate is a silicon substrate.
 272. The waveguide ofclaim 176, wherein the waveguide is formed as a coupler between a fiberand a photodetector or light emittor.
 273. The waveguide of claim 238,wherein the stable material comprises fluorinated cross linking groupsbetween M elements in a three dimensional -M-O-M-O— lattice.
 274. Thewaveguide of claim 273, wherein the organic cross linking group is fullyfluorinated.
 275. The waveguide of claim 238, comprising three or moredifferent organic groups bound to the -M-O-M-O— backbone.
 276. Thewaveguide of claim 238, further comprising a dopant D that is ametalloid or early transition metal and is different from M, and isbound to the -M-O-M-O— lattice and alters the refractive index of thestable material compared to an -M-O-M-O— lattice without a dopant. 277.The waveguide of claim 276, wherein the dopant is an early transitionmetal.
 278. The waveguide of claim 277, wherein the dopant is tantalum,zirconium, germanium or titanium.
 279. The waveguide of claim 276,wherein the dopant is a metalloid.
 280. The waveguide of claim 279,wherein the dopant is germanium.
 281. The waveguide of claim 176,wherein the waveguide is part of an N-port splitter with cascadingY-couplers.
 282. The waveguide of claim 176, wherein the waveguide ispart of a planar crossover.
 283. The waveguide of claim 176, wherein thewaveguide is formed as part of an integrated optical circuit.
 284. Thewaveguide of claim 283, wherein the integrated optical circuit comprisesone or more of a light emittor, a photodetector, an ampliflier and aswitch.
 285. The waveguide of claim 176, wherein the waveguide is formedwithin a multi-device assembly on a single substrate.
 286. The waveguideof claim 285, wherein the multi-device assembly is a wavelength divisionmultiplexor receiver assembly.
 287. The waveguide of claim 286, whereinthe wavelength division multiplexor receiver assembly comprises one ormore arrayed waveguide gratings, an amplifier, and one or more PIN diodereceivers.
 288. The waveguide of claim 285, wherein the multi-deviceassembly comprises a plurality of lasers, a plurality of externalmodulators, a combiner and amplifier.
 289. The waveguide of claim 176,formed proximate to a photodetector or light emittor on the substrate.290. The waveguide of claim 176, wherein the waveguide is formed as acoupler between a fiber and either a photodetector or light emittor.291. The waveguide of claim 176, wherein the stable material is doped.292. The waveguide of claim 291, wherein the dopait is erbium.
 293. Thewaveguide of claim 176, wherein the stable material is a siloxane. 294.The waveguide of claim 176, wherein at least the core layer is thestable layer.
 295. The waveguide of claim 176, wherein at least one ofthe cladding layers is the stable layer.
 296. The waveguide of claim176, further comprising a passivation layer on the upper cladding layer.297. The waveguide of claim 176, wherein the lower cladding layer, theupper cladding layer and the core layer are the stable layers.
 298. Thewaveguide of claim 176, wherein the stable material comprises between 2and 6 different organic substituents on an inorganic three dimensionalbackbone matrix.
 299. The waveguide of claim 238, wherein the molecularweight is from 500 to
 5000. 300. The waveguide of claim 238, wherein themolecular weight is from 500 to
 3000. 301. The waveguide of claim 177,wherein the stable material is fully or partially fluorinated.
 302. Thewaveguide of claim 263, wherein the LED is an OLED.
 303. The waveguideof claim 176, wherein the stable material has an optical loss of 0.1dB/cm at 1550 μm, is deposited at 200 C or less, a polarizationdependent loss of 0.1 dB/cm or less and a surface roughness of 10 nm orless.
 304. The waveguide of claim 176, further comprising forming abuffer layer on the substrate before forming the lower cladding layer.305. The waveguide of claim 304, wherein the buffer layer has ahydrophobicity that results in a contact angle of 90 degrees or more ifexposed to water.
 306. The waveguide of claim 176, wherein the corelayer is formed by depositing a core material followed by patterning thecore material to form an elongated core.
 307. An optical devicecomponent, comprising: a substrate; a waveguide layer, wherein thewaveguide layer comprises a material that is capable of being heated insupercritical water vapor at 2 atm and at 120 C for 2 hours after whichoptical absorption, polarization dependent loss and/or refractive indexchange remains unchanged ±5%.
 308. A method for making a waveguide,comprising: forming a core layer and an upper cladding layer on asubstrate; wherein the core layer and/or upper cladding layer comprisesa material that is capable of being heated in supercritical water vaporat 2 atm and at 120 C for 2 hours after which optical absorption,polarization dependent loss and/or refractive index change remainsunchanged ±5%.
 309. The method of claim 308, wherein the substrate is alight transmissive substrate.
 310. The method of claim 309, wherein thelight transmissive substrate is a plastic, glass, quartz or sapphiresubstrate.
 311. The method of claim 310, wherein the light transmissivesubstrate is quartz.
 312. The method of claim 309, wherein the substrateacts as a lower cladding layer for the waveguide.